CN106187817B - 具有聚集诱导发光性质和压致变色性质的荧光材料 - Google Patents
具有聚集诱导发光性质和压致变色性质的荧光材料 Download PDFInfo
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- 230000002776 aggregation Effects 0.000 title claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 24
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- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical class COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
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- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
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- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
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- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/36—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by hydroxy groups
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Abstract
本发明公开了一类具有聚集诱导发光和压致变色性质的荧光材料,该荧光材料结构式为
Description
技术领域
本发明属于荧光材料技术领域,具体涉及一类具有聚集诱导发光性质和压致变色性质的荧光材料。
背景技术
荧光材料由于在光电器件、环境传感器、生物科学等领域具有重大的应用价值,近年来引起了科学家们的极大关注。传统荧光化合物在溶液中显示很强的荧光,但是大多数在聚集状态时呈现荧光减弱甚至淬灭的现象,即聚集诱导荧光淬灭效应(aggregation-caused quenching,ACQ)。鉴于荧光材料常常被用于聚集或固体薄膜,因此,ACQ现象限制了荧光材料在特定情况下的应用前景。2001年,香港科技大学唐本忠院士课题组发现了一类具有螺旋桨结构的分子具有奇特的发光行为:当该类分子溶解在溶液中时,荧光很弱或是不发光,但在固态或聚集状态时,则产生强烈的荧光。他们把这一现象命名为聚集诱导发光(aggregation-induced emission,AIE)现象。AIE现象与传统的ACQ现象恰好相反,利用这一新特性可以进一步拓宽有机荧光化合物在固体或聚集状态领域的应用。近年来,科学家们努力开发新的AIE体系及其在有机发光二极管、生物探针、化学传感器和细胞成像等领域的应用。由于大多数的具有AIE性质的化合物具有扭曲的分子构象,导致其分子堆积相对松散,在受到外界刺激时由于堆积方式的改变会呈现不同的发光行为,即压致变色性。压致变色是指当受到外力刺激,如加热、溶剂熏蒸或研磨时,材料的荧光(如发光强度、发射波长)随之发生改变的性质。具有压致变色性质的荧光材料是一种新型的智能材料,它在应力传感器、信息存储、荧光开关和发光器件等领域具有非常广泛的应用。但是到目前为止已经报道的具有压致变色性质的发光材料还不是很多,所以设计合成新型的具有压致变色性质的聚集诱导发光材料仍然被迫切需要。
发明内容
本发明所要解决的技术问题在于提供一类具有聚集诱导发光及压致变色效应的新型荧光材料。
解决上述技术问题所采用的技术方案是:该荧光材料的结构式如下所示:
式中Ar代表苯基、C1~C4烷基取代苯基、C1~C4烷氧基取代苯基、4-羟甲基苯基、噻吩基、C1~C4烷基取代噻吩基、呋喃基、羟基取代苯基、卤代苯基、萘基、N-碳酸叔丁酯-2-吡咯基、4-叔丁基二甲基硅氧基苯基中的任意一种,具体如苯基、4-甲基苯基、2-甲基苯基、4-甲氧基苯基、2-甲氧基苯基、2,6-二甲氧基苯基、4-羟甲基苯基、2-噻吩基、5-甲基-2-噻吩基、3-呋喃基、4-羟基苯基、4-氯苯基、4-氟苯基、1-萘基、2-萘基、N-碳酸叔丁酯-2-吡咯基、4-叔丁基二甲基硅氧基苯基等。
上述具有聚集诱导发光性质和压致变色性质的荧光材料(除Ar代表4-叔丁基二甲基硅氧基苯基)的制备方如下:
1、以DMF为溶剂,将2,5-二溴苯-1,4-二甲醛、式I所示的芳基硼酸、醋酸钯按摩尔比为1:2.5:0.05,在碱性条件下室温反应至完全,分离纯化产物,得到式II所示的2,5-二芳基-1,4-二甲醛。
2、以无水乙醇为溶剂,将式II所示的2,5-二芳基-1,4-二甲醛与丙二腈按摩尔比为1:2.05,在碱性条件下室温反应至完全,分离纯化产物,得到荧光材料。
当Ar代表4-叔丁基二甲基硅氧基苯基时,该荧光材料的制备方法为:
1、以DMF为溶剂,将2,5-二溴苯-1,4-二甲醛、4-羟基苯硼酸、醋酸钯按摩尔比为1:2.5:0.05,在碱性条件下室温反应至完全,分离纯化产物,得到4,4”-二羟基-[1,1':4',1”-三联苯]-2',5'-二甲醛。
2、以DMF为溶剂,将4,4”-二羟基-[1,1':4',1”-三联苯]-2',5'-二甲醛与咪唑、叔丁基二甲基氯硅烷(TBDMS-Cl)按摩尔比为1:4:3,室温反应至完全,分离纯化产物,得到式III所示的44”-二甲基叔丁基硅基-[1,1':4',1”-三联苯]-2'5'-二甲醛。
3、以无水乙醇为溶剂,将4,4”-二甲基叔丁基硅基-[1,1':4',1”-三联苯]-2',5'-二甲醛与丙二腈按摩尔比为1:2.05,在碱性条件下室温反应至完全,分离纯化产物,得到荧光材料——1,4-二(4-(2,5-二甲基叔丁基)硅氧基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈。
本发明荧光材料在普通有机溶剂中具有良好的溶解性,而在水中几乎不溶解,可形成纳米聚集体,具有聚集诱导发光特性。同时通过研磨,该类荧光材料的荧光发射波长会向长波方向移动,用二氯甲烷熏蒸后荧光发射波长则会恢复,具有压致变色的性质。
附图说明
图1是实施例1制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图2是实施例1制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图3是实施例2制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图4是实施例2制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图5是实施例3制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图6是实施例3制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图7是实施例4制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图8是实施例4制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图9是实施例6制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图10是实施例6制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图11是实施例7制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图12是实施例7制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图13是实施例8制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图14是实施例8制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图15是实施例9制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图16是实施例9制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图17是实施例10制备的化合物在丙酮与水的混合体系中的荧光发射光谱图。
图18是实施例10制备的化合物在丙酮与水的混合体系中的发射的相对强度图。
图19是实施例2制备的化合物研磨和二氯甲烷熏蒸前后的荧光光谱图。
图20是实施例3制备的化合物研磨和二氯甲烷熏蒸前后的荧光光谱图。
图21是实施例4制备的化合物研磨和二氯甲烷熏蒸前后的荧光光谱图。
图22是实施例5制备的化合物研磨和二氯甲烷熏蒸前后的荧光光谱图。
图23是实施例10制备的化合物研磨和二氯甲烷熏蒸前后的荧光光谱图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
合成结构式如下的1,4-二苯基-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
1、将0.0584g(0.2mmol)2,5-二溴苯-1,4-二甲醛、0.27mL DMF、0.13mL 2mol/LNa2CO3水溶液、0.0609g(0.5mmol)苯硼酸加入到5mL圆底烧瓶中,搅拌10分钟后,向反应液中加入0.0424g(0.01mmol)醋酸钯,待反应完成后,用乙酸乙酯萃取(3×5mL),合并有机相,有机相经无水硫酸钠干燥、过滤、旋干、石油醚与乙酸乙酯的体积比为20:1的混合液柱层析,得到1,1':4',1”-三联苯-2',5'-二甲醛。
2、向25mL圆底烧瓶中加入0.0400g(1.05mmol)1,1':4',1”-三联苯-2',5'-二甲醛,并加入无水乙醇使其溶解,然后加入0.1419g(2.15mmol)丙二腈和0.05mL 1mol/L的NaOH水溶液,在室温下搅拌2.5小时,析出固体,过滤,得到1,4-二苯基-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为71%,结构表征数据为:1H-NMR(400MHz,d6-DMSO)δ(ppm):8.35(s,1H),8.21(s,1H),7.62-7.56(m,3H,Ar H),7.50(d,2H,J=7.3Hz,ArH);13C-NMR(101MHz,d6-DMSO)δ(ppm):160.26,141.51,136.97,132.99,130.77,129.93,129.05,113.58,112.91,87.55,79.19.HRMS(ESI-TOF)m/z:[M+Na]+理论值C26H14N4Na,405.1116,实测值405.1117。
实施例2
合成结构式如下的1,4-二(3-呋喃基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的3-呋喃硼酸替换,其他步骤与实施例1相同,得到1,4-二(3-呋喃基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为63%,结构表征数据为:1H-NMR(300MHz,CDCl3)δ(ppm):8.24(s,1H),8.05(s,1H),7.64(t,1H,J=1.6Hz),7.55(s,1H),6.62-6.61(q,1H);13C-NMR(101MHz,CDCl3)δ(ppm):157.36,145.09,142.34,134.28,132.85,130.21,122.40,112.82,111.99,111.35,87.65.HRMS(ESI-TOF)m/z:[M+Na]+理论值C22H10N4O2Na,385.0701,实测值385.0703。
实施例3
合成结构式如下的1,4-二(4-甲氧基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的4-甲氧基苯硼酸替换,其他步骤与实施例1相同,得到1,4-二(4-甲氧基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为69%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.22(s,1H),7.84(s,1H),7.27(d,2H,J=8.5Hz,Ar H),7.07(d,2H,J=8.5Hz,Ar H),3.91(s,3H,CH3);13C-NMR(101MHz,CDCl3)δ(ppm):160.97,158.77,142.91,132.79,131.50,130.76,128.94,115.03,113.09,112.29,86.53,55.69.HRMS(ESI-TOF)m/z:[M+Na]+理论值C28H18N4O2Na,465.1327,实测值465.1330。
实施例4
合成结构式如下的1,4-二(4-羟甲基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的4-羟甲基苯硼酸替换,其他步骤与实施例1相同,得到1,4-二(4-羟甲基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为40%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.32(s,1H),8.19(s,1H),7.53(d,2H,J=8.0Hz,Ar H),7.45(d,2H,J=8.0Hz,Ar H),5.34(t,1H,J=5.7Hz),4.61(d,2H,J=5.6Hz,CH2);13C-NMR(100MHz,CDCl3)δ(ppm):160.24,143.04,141.41,135.26,132.90,130.61,129.92,113.58,112.86,87.28,62.48。
实施例5
合成结构式如下的1,4-二(2-噻吩基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的2-噻吩硼酸替换,其他步骤与实施例1相同,得到1,4-二(2-噻吩基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为64%,结构表征数据为:1H-NMR(300MHz,d6-DMSO)δ(ppm):8.60(s,1H),8.25(s,1H),7.90(d,1H,J=4.5Hz),7.38-7.31(m,2H);13C-NMR(100MHz,d6-DMSO)δ(ppm):160.06,138.76,134.41,133.12,131.45,131.11,130.65,129.53,114.12,113.24,88.87。
实施例6
合成结构式如下的1,4-二(4-羟基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的4-羟基苯硼酸替换,其他步骤与实施例1相同,得到1,4-二(4-羟基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为45%,结构表征数据为:1H-NMR(400MHz,d6-DMSO)δ(ppm):9.95(s,1H),8.30(s,1H),8.10(s,1H),7.28(d,2H,J=8.5Hz,Ar H),6.96(d,2H,J=8.5Hz,Ar H);13C-NMR(101MHz,d6-DMSO)δ(ppm):160.61,158.44,140.90,132.61,131.35,130.24,127.63,115.84,113.71,113.02,86.61.HRMS(ESI-TOF)m/z:[M+Na]+理论值C26H14N4O2Na,437.1014,实测值437.1017。
实施例7
合成结构式如下的1,4-二(5-甲基-2-噻吩基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的5-甲基-2-噻吩硼酸(0.0710g)替换,其他步骤与实施例1相同,得到1,4-二(5-甲基-2-噻吩基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为75%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.21(s,1H),8.07(s,1H),6.89(s,2H),2.58(s,3H,CH3);13C-NMR(75MHz,CDCl3)δ(ppm):157.93,145.48,135.83,1 50,132.32,130.89,130.77,127.40,113.02,111.95,87.32,15.67.HRMS(ESI-TOF)m/z:[M+Na]+理论值C24H14N4S2Na,445.0558,实测值445.0563。
实施例8
合成结构式如下的1,4-二(2,5-二甲氧基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的2,6-二甲氧基苯硼酸替换,其他步骤与实施例1相同,得到1,4-二(2,5-二甲氧基苯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为87%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.14(s,1H,),7.63(s,1H,),7.45-7.41(t,2H,J=8.4Hz,ArH),6.70(d,2H,J=8.4Hz,ArH),3.79(s,6H,CH3);13C-NMR(101MHz,CDCl3)δ(ppm):160.18,157.73,136.20,134.61,132.01,131.66,113.78,113.37,112.03,104.24,84.80,55.98。
实施例9
合成结构式如下的1,4-二(N-碳酸叔丁酯-2-吡咯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将实施例1中的苯硼酸用等物质的量的N-碳酸叔丁酯-2-吡咯硼酸(0.1055g)替换,其他步骤与实施例1相同,得到1,4-二(N-碳酸叔丁酯-2-吡咯基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为59%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.17(s,1H),7.68(s,1H),7.46-7.45(t,2H,J1=2.6Hz,J2=2.2Hz,CH),6.35(d,2H,J=3.1Hz,CH),1.47(s,9H,CH3);13C-NMR(101MHz,CDCl3)δ(ppm):158.87,157.44,142.93,132.73,131.51,130.77,139.48,121.01,113.07,112.31,86.48,25.77,18.37,-4.16.HRMS(ESI-TOF)m/z:[M+Na]+理论值C32H28N6O4Na,538.2070,实测值538.2074。
实施例10
合成结构式如下的1,4-二(4-(2,5-二甲基叔丁基)硅氧基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈
将0.0584g(0.2mmol)2,5-二溴苯-1,4-二甲醛、0.27mL DMF、0.13mL2mol/L Na2CO3水溶液、0.0690g(0.5mmol)4-羟基苯硼酸加入到5mL圆底烧瓶中,搅拌10分钟后,向反应液中加入0.0424g(0.01mmol)醋酸钯,待反应完成后,用乙酸乙酯萃取(3×5mL),合并有机相,有机相经无水硫酸钠干燥、过滤、旋干、石油醚与乙酸乙酯的体积比为10:1的混合液柱层析,得到4,4”-二羟基-[1,1':4',1”-三联苯]-2',5'-二甲醛。
2、向25mL圆底烧瓶中加入0.03g(0.094mmol)4,4”-二羟基-[1,1':4',1”-三联苯]-2',5'-二甲醛和5mL DMF,室温下搅拌使其完全溶解,再加入0.026g(0.376mmol)咪唑和0.043g(0.282mmol)叔丁基二甲基氯硅烷(TBDMS-Cl),室温下搅拌过夜,反应完成后,加入10mL蒸馏水,然后用乙酸乙酯(3×8mL)萃取,合并有机相,有机相经无水硫酸钠干燥、过滤,旋干、石油醚与乙酸乙酯的体积比为20:1的混合液柱层析,得到4,4”-二甲基叔丁基硅基-[1,1':4',1”-三联苯]-2',5'-二甲醛。
3、向25mL圆底烧瓶中加入0.5480g(1mmol)4,4”-二甲基叔丁基硅基-[1,1':4',1”-三联苯]-2',5'-二甲醛,并加入无水乙醇使其溶解,然后加入0.1353g(2.05mmol)丙二腈和0.05mL 1mol/L的NaOH水溶液,在室温下搅拌2.5小时,过滤,得到1,4-二(4-(2,5-二甲基叔丁基)硅氧基)-2,2'-(1,4-亚苯基二(亚甲基))丙二腈,其产率为82%,结构表征数据为:1H-NMR(400MHz,CDCl3)δ(ppm):8.21(s,1H),7.85(s,1H),7.20(d,2H,J=8.5Hz,ArH),7.01(d,2H,J=8.5Hz,ArH),1.02(s,9H,CH3),0.28(s,6H,CH3);13C-NMR(101MHz,CDCl3)δ(ppm):158.87,157.43,142.93,132.73,131.51,130.77,129.48,121.00,113.07,112.31,86.49,25.77,18.37,-4.16.HRMS(ESI-TOF)m/z:[M+Na]+理论值C38H42N4O2Si2Na,665.2744,实测值665.2745。
发明人将实施例1~4及6~10制备的化合物分别与丙酮和蒸馏水按不同体积比混合,采用日立F-7000荧光分光光度计测试混合体系的AIE性质,结果见图1~18。由图可见,此类化合物均具有聚集诱导发光性质。
发明人采用日立F-7000荧光分光光度计测试实施例2、3、4、5、10制备的化合物的压致变色性质,结果见图19~23。由图可见,实施例2、3、4、5、10制备的化合物的粉末荧光发射峰分别位于543nm、510nm、526nm、562nm、513nm处。当分别将其研磨后,光谱发生红移,最大发射峰位分别在543nm、544nm、562nm、574nm、527nm,半峰宽也出现增大趋势。研磨后的样品用二氯甲烷熏蒸后,发射峰位置又转变为与原始样品几乎一致。再次将其研磨,则又回到第一次研磨后的发射峰位置,说明此类化合物具有典型的压致变色性质。
Claims (1)
1.一类具有聚集诱导发光和压致变色性质的荧光材料,其特征在于该荧光材料的结构式如下所示:
式中Ar代表4-甲氧基苯基、4-羟甲基苯基、3-呋喃基、4-叔丁基二甲基硅氧基苯基中的任意一种。
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