CN115557942A - 一种具有多重刺激响应的发光材料及制备方法和应用 - Google Patents
一种具有多重刺激响应的发光材料及制备方法和应用 Download PDFInfo
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Abstract
Description
技术领域
本申请涉及光电功能材料技术领域,主要涉及一种具有多重刺激响应的发光材料及制备方法和应用。
背景技术
近年来,有机发光材料已广泛应用于通讯、显示、记录、传感和成像等与国计民生息息相关的领域。发光材料的颜色(波长)、效率和寿命等性质对构筑高性能的光电器件及应用起着至关重要的作用。然而,传统的发光材料通常只表现出单一的发光特征,从而导致材料资源的匮乏和多功能的限制。自智能材料的概念被提出以来,刺激响应型可调控发光材料,亦称为智能发光材料,因其发光性质对外界环境刺激(包括热、光、电、力、化学等刺激)敏感变化的特性,在应力观测、显示显像、信息安全及存储、传感器等领域展现出极大的应用前景,受到人们越来越广泛的关注和重视。
在取得显著进展的同时,刺激响应型智能发光材料依旧存在许多问题亟待解决:
目前已经报道的刺激响应发光分子普遍具有单一响应的特点,难以满足多元化的应用需求;多数刺激响应发光分子只具有双色变化,在实现快速、可逆、高反差多色变化方面差强人意;而同时具有多重刺激响应和多光色转换的材料更是有限,在一种材料中集成多模式发光仍然是极具挑战性的工作。
另外,多数发光分子需要复杂冗长的合成或昂贵的贵金属作为原料,制备成本距离实际应用具有相当大的距离。相对于基于贵金属配合物的刺激响应型智能发光材料的大量研究,基于廉价的过渡金属(如锌、镍和铜等)配合物的刺激响应性和可控发光的报道还十分有限,实际上,这些过渡金属配合物具有原料成本低、合成简便及丰富的发光性能优势,因此,开发基于经济的过渡金属配合物的智能发光材料是实现低成本智能器件应用的有效途径。
传统刺激响应荧光材料还存在激子利用率低的缺陷,开发激子利用率高的刺激响应荧光材料具有重要意义。目前,热活化延迟荧光(TADF)材料由于其较高的激子利用率而受到广泛关注。在热能的帮助下,其最低激发三线态(T1)激子能够克服能垒经过反系间窜越(RISC)到达最低激发单线态(S1)进行发光,从而获得较高的激子利用率。由于TADF分子的RISC过程对热和氧气都高度敏感,还可应用于温度和氧气传感中。然而,具有TADF特性的刺激响应荧光材料非常有限。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本申请的目的在于提供一种具有多重刺激响应的发光材料及制备方法和应用,旨在解决现有发光材料刺激响应类型单一的问题。
本申请的技术方案如下:
一种具有多重刺激响应的发光材料,其中,具有如式(I)所示的化学结构:
其中,A为电子受体扩展核,D为电子给体基团。
本申请提供的具有多重刺激响应的发光材料,是一类基于席夫碱锌化合物的新型刺激响应变色材料,此类席夫碱锌配合物具有路易斯酸性,还具有正交分布的非共价相互作用,可利用不同方向驱动力之间的“相互竞争”可诱导多种分子组装形态产生,此外,还通过构筑特定的给-受体(D-A)分子结构,将热活化延迟荧光(TADF)特性引入到本申请的发光材料中。本申请的发光材料具有独特光物理性质,灵活的结构可调性以及生产成本低等优势,是一类优异的多重刺激响应型智能发光材料。
所述的具有多重刺激响应的发光材料,其中,所述A为式(A-1)~式(A-5)中任一所示的结构。
选用以上结构的电子受体扩展核,一方面这些受体基团具有较强的吸电子特征,这些受体基团的引入可以增加发光材料目标分子的偶极,增强分子内电荷转移特性,分子内电荷转移效应对环境敏感变化及对分子间相互作用、分子构象和堆积结构强烈依赖的特点有助于高效刺激响应行为的实现。另一方面,π共轭芳环或芳杂环有利于构筑刚性中心骨架,并且还可以对外围取代基(F或者CN)进行适当修饰,诱导分子间π-π或氢键等多种类型的超分子弱相互作用的产生,具有丰富的非共价相互作用的分子体系,可以为发光材料的多重刺激响应性提供更多机会。
所述的具有多重刺激响应的发光材料,其中,所述D为式(D-1)~式(D-18)中任一所示的结构。
所述的具有多重刺激响应的发光材料,其中,所述具有多重刺激响应的发光材料为式(1)~(168)所示的化合物中的一种。
一种如上所述的具有多重刺激响应的发光材料的制备方法,其中,包括以下步骤:
以乙醇为溶剂,加入第一原料、第二原料、二水合醋酸锌,加热回流反应得到所述具有多重刺激响应的发光材料;
所述的具有多重刺激响应的发光材料的制备方法,其中,所述第一原料为式(a1)~(a8)所示的化合物中的一种。
所述的具有多重刺激响应的发光材料的制备方法,其中,所述第二原料为式(d1)~(d21)所示的化合物中的一种。
所述的具有多重刺激响应的发光材料的制备方法,其中,所述第一原料、所述第二原料、所述二水合醋酸锌的摩尔比为1:2:1。
所述的具有多重刺激响应的发光材料的制备方法,其中,加热的温度范围为80~120℃,反应的时间范围为4~12小时。
一种如上所述的具有多重刺激响应的发光材料的应用,其中,将所述具有多重刺激响应的发光材料用于制备传感器、信息存储器件、防伪材料、记忆材料或生物探针。
有益效果:本申请的具有多重刺激响应的发光材料,具有多重组装特性及TADF特性,表现出多重刺激(如力、化学试剂、温度、氧气等)响应的发光特性;并且,本申请的具有多重刺激响应的发光材料具有原料成本低、合成简便、应用环境广、多色可逆切换、高对比度的优势,在传感器、信息安全及存储、智能控制开关和生物医学等与国计民生息息相关的领域表现出广阔的应用前景。
附图说明
图1为本申请实施例中化合物的压致变色测试的结果图。
具体实施方式
本申请提供一种具有多重刺激响应的发光材料及制备方法和应用,为使本申请的目的、技术方案及效果更加清楚、明确,以下对本申请进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本申请,并不用于限定本申请。
本申请提供一种具有多重刺激响应的发光材料,是一类基于席夫碱锌化合物的新型刺激响应变色材料,此类席夫碱锌配合物具有路易斯酸性,可与各种路易斯碱基或酚氧原子进行配位形成加合物,促进化学刺激响应产生,并且分子间不同的Zn…O作用模式可以改变分子的聚集状态;本申请的发光材料分子还具有正交分布的非共价相互作用,利用不同方向驱动力之间的“相互竞争”可诱导多种分子组装形态产生,由于化合物的发光性能对其分子聚集组装结构具有强烈的依赖性,基于非共价键的动态可逆性,在一定环境刺激(如加热、溶剂气氛及压力等)下发光材料分子可以自发且连续的进行组装和去组装,使发光性质的转变具有良好的可逆性和重复性;此外,通过构筑特定的给-受体(D-A)分子结构,将热活化延迟荧光(TADF)特性引入到本申请的发光材料中,不仅有效提高了本申请的发光材料的激子利用率,并且由于TADF分子的RISC过程对热和氧气都高度敏感,使得本申请的发光材料不仅对力、化学试剂、热等刺激敏感响应,也对热和氧气高度敏感,可用于温度或氧气传感。本申请的发光材料具有独特光物理性质,灵活的结构可调性以及生产成本低等优势,是一类优异的多重刺激响应型智能发光材料。
具体地,本申请的具有多重刺激响应的发光材料,具有如式(I)所示的化学结构:
A为电子受体(Acceptor)扩展核,A可以为式(A-1)~式(A-5)中任一所示的结构:
其中,*代表连接位点,X可以为S或Se中的一种,Ra可以为H、F或CN取代基中的一种。
选用以上结构的电子受体扩展核,一方面这些受体基团具有较强的吸电子特征,这些受体基团的引入可以增加发光材料目标分子的偶极,增强分子内电荷转移效应特性,分子内电荷转移效应对环境敏感变化及对分子间相互作用、分子构象和堆积结构强烈依赖的特点有助于高效刺激响应行为的实现。另一方面,π共轭芳环或芳杂环有利于构筑刚性中心骨架,并且还可以对外围取代基(F或者CN)进行适当修饰,诱导分子间π-π或氢键等多种类型的超分子弱相互作用的产生,具有丰富的非共价相互作用的分子体系,可以为发光材料的多重刺激响应性提供更多机会。
D为电子给体( Donor )基团,D可以为式(D-1)~式(D-18)中任一所示的结构:
其中,虚线代表连接位点,Rb可以是H、苯基、含有1-16个碳的直链或带支链的烷基、含有1-16个碳的直链或带支链的烷氧基中的一种。
以上结构的电子给体是构筑TADF特性分子比较常用的给体基团,给受体之间相互扭曲的分子构型,为激发态电子能量转移提供了可能路径,带来新的发光现象;这些给体基团的空间位阻效应还可以起到抑制分子聚集猝灭的作用,提高发光材料的发光效率;并且,不同类型给体基团的引入起到调节发光材料的光电性质的作用。
在一个或多个实施方式中,本申请的具有多重刺激响应的发光材料优选为式(1)~(168)所示的化合物但不限于如下化合物:
本申请的具有多重刺激响应的发光材料,属于电子给-受体型发光材料,本申请中还提供该具有多重刺激响应的发光材料的制备方法,其合成路线如式(II)所示:
合成目标化合物的主要前驱体原料为电子受体A二胺(第一原料)和电子给体D取代水杨醛(第二原料),经过加入二水合醋酸锌,以乙醇为溶剂加热回流反应得到。
在本申请实施例方案中,第一原料:第二原料:二水合醋酸锌的摩尔比可以为1:2:1。乙醇为溶剂,对其用量没有特殊限制。加热回流时,加热温度以超过乙醇沸点的温度为适当温度,优选为80~120℃之间,反应时间为4~12小时。
其中,制备式(1)~(168)所示的化合物所需的第一原料,可以选自以式(a1)~(a8)所示的化合物中的一种:
制备式(1)~(168)所示的化合物所需的第二原料,可以选自以式(d1)~(d21)所示的化合物中的一种:
本申请的具有多重刺激响应的发光材料,具有多重组装特性及TADF特性,表现出多重刺激(如力、化学试剂、温度、氧气等)响应的发光特性;并且,本申请的具有多重刺激响应的发光材料具有原料成本低、合成简便、应用环境广、多色可逆切换、高对比度的优势,在传感器、信息安全及存储、智能控制开关和生物医学等与国计民生息息相关的领域表现出广阔的应用前景。
本申请中还提供具有多重刺激响应的发光材料的应用,将本申请的具有多重刺激响应的发光材料用于制备传感器、信息存储器件、防伪材料、记忆材料、生物探针等。
以下通过具体实施例对本申请作进一步说明。
本申请对以下实施例中所采用的原料的来源没有特别的限制,可为市售产品或采用本领域技术人员所熟知的制备方法制备得到。
依照式(II)所示合成路线,制备式(1)~(168)所示的化合物,以下给出化合物3、化合物4、化合物11、化合物26、化合物29、化合物44、化合物51、化合物64的具体合成过程。
合成实施例1:化合物3
氮气保护下,向双口瓶中分别加入苯并[c][1,2,5]噻二唑-5,6-二胺(原料a1)(166 mg, 1 mmol),2-羟基-4-(10H-吩噁嗪-10-基)苯甲醛(原料d3)(607 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到橙色固体产物(720 mg, 产率90%)。质谱:798.10,元素分析:C, 66.05; H, 3.28; N,10.50; O, 8.00; S, 4.01; Zn, 8.17。
合成实施例2:化合物4
氮气保护下,向双口瓶中加入苯并[c][1,2,5]噻二唑-5,6-二胺(原料a1)(166mg, 1 mmol),2-羟基-4-(10H-吩噻嗪-10-基)苯甲醛(原料d4)(639 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到橙色固体产物(766 mg, 产率92%)。质谱:830.06 ,元素分析:C, 63.50; H, 3.15; N,10.10; O, 3.84; S, 11.56; Zn, 7.86。
合成实施例3:化合物11
氮气保护下,向双口瓶中加入苯并[c][1,2,5]噻二唑-5,6-二胺(原料a1)(166mg, 1 mmol),2-羟基-4-(3,6-二叔丁基咔唑)苯甲醛(原料d11)(798 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(852 mg, 产率86%)。质谱:990.36,元素分析:C, 72.60; H, 5.89; N, 8.47;O, 3.22; S, 3.23; Zn, 6.59。
合成实施例4:化合物26
氮气保护下,向双口瓶中加入苯并[c][1,2,5]硒二唑-5,6-二胺(原料a2)(166mg, 1 mmol),2-羟基-4-( 9,9-二甲基吖啶)苯甲醛(原料d5)(658 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到橙黄色固体产物(763 mg, 产率85%)。质谱:898.15,元素分析:C, 66.78; H, 4.26; N, 9.35;O, 3.56; Se, 8.78; Zn, 7.27。
合成实施例5:化合物29
氮气保护下,向双口瓶中加入苯并[c][1,2,5]硒二唑-5,6-二胺(原料a2)(166mg, 1 mmol),2-羟基-4-(3,7-二甲基-10H-吩噁嗪-10-基)苯甲醛(原料d8)(662 mg, 2mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到橙色固体产物(803mg, 产率89%)。质谱:902.11,元素分析:C, 63.83; H,3.79; N, 9.31; O, 7.09; Se, 8.74; Zn, 7.24。
合成实施例6:化合物44
氮气保护下,向双口瓶中加入4,7-二氟-苯并[c][1,2,5]噻二唑-5,6-二胺(原料a3)(202 mg, 1 mmol),4-二苯胺基苯甲醛(原料d2)(578 mg, 2 mmol),二水合醋酸锌(220mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(709 mg, 产率88%)。质谱:806.13,元素分析:C, 65.39; H, 3.49; N, 10.40; O, 3.96;S, 3.97; Zn, 8.09。
合成实施例7:化合物51
氮气保护下,向双口瓶中加入4,7-二氟-苯并[c][1,2,5]噻二唑-5,6-二胺(原料a3)(202 mg, 1 mmol),2-羟基-4-(3,7-二甲基-10H-吩噻嗪-10-基)苯甲醛(原料d9)(694mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(784 mg, 产率85%)。质谱:922.10,元素分析:C, 62.37;H, 3.49; F, 4.11; N, 9.09; O, 3.46; S, 10.40; Zn, 7.07。
合成实施例8:化合物64
氮气保护下,向双口瓶中加入4,7-二氰基-苯并[c][1,2,5]噻二唑-5,6-二胺(原料a4)(216 mg, 1 mmol),2-羟基-4-(3,7-二甲基-10H-吩噻嗪-10-基)苯甲醛(原料d1)(574 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(677 mg, 产率83%)。质谱:816.10,元素分析:C,67.53; H, 2.96; N, 13.70; O, 3.91; S, 3.92; Zn, 7.99。
合成实施例10:化合物69
氮气保护下,向双口瓶中加入4,7-二氰基-苯并[c][1,2,5]噻二唑-5,6-二胺(原料a4)(216 mg, 1 mmol),4-(9,9-二苯基吖啶)-2-羟基苯甲醛(原料d6)(906 mg, 2mmol),二水合醋酸锌(220 mg, 1 mmol),以100 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(959 mg, 产率81%)。质谱:1148.26,元素分析:C,75.16; H,3.85; N,9.74; O,2.78; S,2.79; Zn,5.68。
合成实施例11:化合物94
氮气保护下,向双口瓶中加入1,2,3,4-四氰基-5,6-二氨基苯(原料a5)(208 mg,1 mmol),4-(2,7,9,9-四甲基吖啶)-2-羟基苯甲醛(原料d10)(714 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(677 mg, 产率85%)。质谱:948.29,元素分析:C,73.30; H,4.67; N,11.79; O,3.37; Zn,6.88。
合成实施例12:化合物101
氮气保护下,向双口瓶中加入1,2,3,4-四氰基-5,6-二氨基苯(原料a5)(208 mg,1 mmol),4-(9-苯基咔唑)-2-羟基苯甲醛(原料d17)(726 mg, 2 mmol),二水合醋酸锌(220mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(835 mg, 产率87%)。质谱:960.19,元素分析:C,74.89; H,3.35; N,11.64; O,3.32; Zn,6.79。
合成实施例13:化合物112
氮气保护下,向双口瓶中加入5,6-二氨基-2,3-二氰基吡嗪(原料a6)(160 mg, 1mmol),4-(9,9-螺芴基吖啶)-2-羟基苯甲醛(原料d7)(902 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以100 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(860 mg, 产率79%)。质谱:1088.26,元素分析:C,77.10; H,3.70; N,10.28; O,2.93;Zn,6.00。
合成实施例14:化合物124
氮气保护下,向双口瓶中加入5,6-二氨基-2,3-二氰基吡嗪(原料a6)(160 mg, 1mmol),4-(10-苯基吩噁嗪)-2-羟基苯甲醛(原料d19)(758 mg, 2 mmol),二水合醋酸锌(220 mg, 1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(774 mg, 产率82%)。质谱:944.18,元素分析:C,71.08; H,3.41; N,11.84; O,6.76;Zn,6.91。
合成实施例15:化合物137
氮气保护下,向双口瓶中加入6,7-二氨基喹喔啉(原料a7)(160 mg, 1 mmol),2-羟基-4-(3,6-二叔丁基咔唑)苯甲醛(原料d11)(798 mg, 2 mmol),二水合醋酸锌(220 mg,1 mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(774mg, 产率88%)。质谱:984.41,元素分析:C,75.48; H,6.13; N,8.52; O,3.24; Zn,6.63。
合成实施例17:化合物167
氮气保护下,向双口瓶中加入2,3-二氨基喹喔啉(原料a8)(160 mg, 1 mmol),4-(10-苯基吩噻嗪)-2-羟基苯甲醛(原料d20)(790 mg, 2 mmol),二水合醋酸锌(220 mg, 1mmol),以80 mL乙醇做溶剂,80℃反应6小时。冷却,将析出的固体用布氏漏斗过滤,乙醇洗涤,滤饼用乙醇和二氯甲烷混合液(体积比3:1)重结晶后,烘干得到黄色固体产物(791 mg,产率81%)。质谱:976.16,元素分析:C,71.20; H,3.71; N,8.59; O,3.27; S,6.55; Zn,6.68。
依照式(II)所示合成路线,制备式(1)~(168)所示的化合物,产物数据汇总如表1-5所示。
表1
表2
表3
表4
表5
选取化合物1、化合物4、化合物32、化合物129进行刺激响应发光测试:(1)分别测试化合物研磨前原始固体的发射波长、研磨后的发射波长、对研磨后的化合物进行加热后的发射波长、对研磨后的化合物在二氯甲烷溶剂气氛下的发射波长,结果如表6所示;(2)将化合物溶于甲苯溶液中,分别测试化合物在甲苯溶液中的发射波长及发光效率,然后对甲苯溶液进行鼓氮气,分别测试化合物在甲苯溶液鼓氮气后的发射波长及发光效率,结果如表6所示。
研磨前化合物在自然光下呈绿色,经过研磨后,颜色变为红色,经过加热后(加热温度可以为115~130℃,加热时间可以为1~3分钟,在本申请实施例方案中,120℃加热1分钟),颜色变为黄色。将研磨后的化合物在二氯甲烷溶剂气氛下熏蒸,颜色变回绿色。这说明化合物具有典型的显著的多色及多重刺激响应发光变色效应。
将化合物溶于甲苯溶液中,在自然光下呈绿色,经过鼓氮气后,颜色不变,但发光效率得到提高。这说明化合物具有TADF特性,发光对氧气敏感,鼓氮气除氧后,化合物延迟荧光组分得到增强,导致发光效率提高。
表6
选取化合物3为测试对象,进行温度依赖的发光性质测试,测试不同温度下的光致发光效率、寿命。用真空蒸镀法将化合物3蒸镀在石英片上,化合物3的薄膜厚度约50nm,对化合物3的薄膜进行不同温度下的时间分辨荧光光谱测试,结果如表7所示,其中,ΦPL表示光致荧光量子效率、Φp表示瞬时荧光量子效率、Φd表示延迟荧光量子效率、τp (ns)表示瞬时荧光寿命、τd (μs)表示延迟荧光寿命。从结果可以看出延迟荧光组分的荧光量子效率及所占比重随温度从100K到300K明显增强,由于温度升高后,热能促使分子的T1到S1的RISC过程加快,导致延迟组分增加。化合物的瞬态荧光衰减光谱包括瞬时和延迟双组分,延迟荧光组分的荧光量子效率及所占比重是指延迟荧光量子效率Φd,及,延迟荧光量子效率Φd占光致荧光量子效率ΦPL的比重。并且延时荧光寿命随温度变化明显下降,这种温度依赖的发光性质可以用于温度传感应用。
表7
选取化合物1为测试对象,进行压致变色测试,结果如图1所示。将滤纸浸入化合物1的四氢呋喃溶液(浓度为1*10-4M)中,取出滤纸进行干燥,得到绿色的滤纸;在该滤纸上书写字母“Zn”, 可以清楚地看到字母“Zn”显示红色,与背景色颜色差异明显;将书写完的滤纸暴露在四氢呋喃蒸汽中一段时间(1-3分钟左右),可以看到字迹颜色消失,滤纸恢复背景色绿色;拿出滤纸干燥后,再次书写字母“wang”,又可以清楚地看到红色字母“wang”;将书写完的滤纸暴露在四氢呋喃蒸汽中一段时间(1-3分钟左右),字迹颜色将再次消失,恢复背景色绿色。这些结果可以表明化合物在数据安全保护、信息加密-解密处理中方面的应用潜力。
应当理解的是,本申请的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本申请的保护范围。
Claims (10)
8.根据权利要求5所述的具有多重刺激响应的发光材料的制备方法,其特征在于,所述第一原料、所述第二原料、所述二水合醋酸锌的摩尔比为1:2:1。
9.根据权利要求5所述的具有多重刺激响应的发光材料的制备方法,其特征在于,加热的温度范围为80~120℃,反应的时间范围为4~12小时。
10.一种如权利要求1~4任一所述的具有多重刺激响应的发光材料的应用,其特征在于,将所述具有多重刺激响应的发光材料用于制备传感器、信息存储器件、防伪材料、记忆材料或生物探针。
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