CN114409591B - 一种双酰肼紫精衍生物及其制备方法和湿度传感应用 - Google Patents

一种双酰肼紫精衍生物及其制备方法和湿度传感应用 Download PDF

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CN114409591B
CN114409591B CN202210104702.9A CN202210104702A CN114409591B CN 114409591 B CN114409591 B CN 114409591B CN 202210104702 A CN202210104702 A CN 202210104702A CN 114409591 B CN114409591 B CN 114409591B
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bishydrazide
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吴舒婷
许毓茹
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Abstract

本发明公开了一种双酰肼紫精衍生物及其制备方法和湿度传感的应用。所述双酰肼紫精衍生物具有合成条件温和、原料价格适中、产率高的特点。研究发现，该双酰肼紫精衍生物在极度干燥环境下为淡黄色粉末，颜色随环境湿度升高而逐渐呈现灰绿色，湿度100%时为蓝紫色。环境湿度变化时，颜色可在一定湿度范围内可逆变化。

Description

一种双酰肼紫精衍生物及其制备方法和湿度传感应用
技术领域
本发明属于晶态功能材料领域，具体涉及一种以颜色变化作为检测信号的湿度传感材料及其制备方法。
背景技术
对外加刺激有显色反应的刺激致变色材料，因其优异的性质，数十年来得到科学家们的青睐，并在商业、工业等多方面得到广泛应用。引起这些材料具有显色性能的刺激源包括光照、机械应力、温度变化、水的吸附与解吸、外加电压等。紫精是一类1,1’-二取代-4,4’-联吡啶盐衍生物，上世纪，Michaclis团队首次报道甲基紫精在还原态时显紫色，并将其称作紫精。此后，科研工作者普遍将联吡啶盐类的衍生物统称为紫精类化合物。缺电子性的紫精化合物拥有良好的氧化还原性能，在外界物理或化学刺激下可表现出三种不同的氧化还原态，并在此过程中伴随着明显的颜色改变。此外，低能量的LUMO允许紫精衍生物的无机离子（给体）到有机基团（受体）之间发生CT（电荷转移），而这也导致了紫精颜色的多变性。自上世纪被报道以来，此类化合物一直活跃在变色材料的舞台上，比如光致变色、电致变色、压致变色等化学传感器材料的探索研究，被广泛应用于传感器、防伪材料、生物医药标记物等领域。
事实上，紫精化合物由于合成简单，在材料应用具有价格优势。通常，紫精类化合物的变色传感大多由于其在V2+和V·+之间具有明显的颜色区分度，使其传感变色过程很容易通过紫外可见光谱甚至裸眼观察来进行检测。作为刺激紫精产生变色响应的刺激源之一的H2O，被认为是弱的电子供体，不容易诱导紫精衍生物的CT过程。同时在大多数针对紫精湿度传感的文献报道中，分子由于从环境中获得H2O，导致紫精自由基的猝灭。且这类化合物的失水条件相对苛刻，需要通过加热等手段才能使水脱附。因此，研究开发具有在温和的条件下对环境湿度变化敏感的湿度传感材料，具有重要意义。
本发明设计并合成了一种新颖的基于酰肼基紫精衍生物的湿度传感材料L：在一定空气相对湿度（下文用RH表示）变化范围内，对RH有着检测能力。当RH值从100%降至60%时，颜色由蓝紫色变成灰绿色，且当RH在100-60%范围内时可实现颜色的可逆转变。当湿度小于60%时，颜色变成淡黄色。在一定RH范围内，实现对环境湿度的可逆传感变色。
发明内容
本发明的目的在于开发一种双酰肼紫精衍生物及其制备方法和作为湿度传感材料的应用。本发明以自行设计合成的水杨酰肼基紫精衍生物来制备湿度传感材料，使得该材料具有检测湿度RH的能力。本发明的原料廉价易得、方法简单、制备过程快。
为实现上述目的，本发明采用如下技术方案：
一种双酰肼紫精衍生物，其结构式为：
。分子式：C19H17F6N4O3P。命名为：1-(2-(2-(2-hydroxybenzoyl)hydrazinyl)-2-oxoethyl)-[4,4'-bipyridin]-1-iumhexafluorophosphate(V)（下文中简写为L）
进一步的，所述的双酰肼紫精衍生物的制备方法：以2-羟基苯甲酰肼、氯乙酰氯和4,4’-联吡啶为原料制备而成。
具体包括以下步骤：
1）将2-羟基苯甲酰肼和氯乙酰氯混合，以三乙胺为催化剂，以THF为溶剂，冰浴30min，然后在60℃下回流2h，得到OH-Ph-Cl；
2）在OH-Ph-Cl中加入4,4’-联吡啶，以KI和18-冠醚-6为催化剂，以乙腈为溶剂，90℃加热回流反应后，除去溶剂，用乙腈和甲醇洗涤粗产物；将粗产物溶于水中，加入过量的NH4PF6进行阴离子交换，搅拌片刻后得到蓝紫色晶体，为双酰肼紫精衍生物的含水相，将上述晶体干燥得到淡黄色晶体，为双酰肼紫精衍生物的无水相。
应用：所述的双酰肼紫精衍生物在制备湿度传感材料中的应用。
本发明的显著优点在于：
本发明的合成简单、易操作。产品可以灵敏检测RH的变化。本发明合成的双酰肼紫精衍生物，在一定空气相对湿度（下文用RH表示）变化范围内，对RH有着检测能力。当RH值从100%降至60%时，颜色由蓝紫色变成灰绿色，且当RH在100-60%范围内时可实现颜色的可逆转变。当湿度小于60%时，颜色变成淡黄色。在一定RH范围内，实现对环境湿度的可逆传感变色。
附图说明
图1为双酰肼紫精衍生物L的核磁氢谱（以氘代DMSO为溶剂）；
图2为双酰肼紫精衍生物L的湿度传感照片和含水相的单晶结构图；
图3为双酰肼紫精衍生物L的含水相（RH=100%）与无水相的热分析对比图；
图4为双酰肼紫精衍生物L的含水相与无水相的电子顺磁共振谱对比图；
图5为双酰肼紫精衍生物L的含水相与无水相的固体紫外可见漫反射光谱对比图。
具体实施方式
本发明用下列实施例来进一步说明本发明，但本发明的保护范围并不限于下列实施例。
实施例1
水杨酰肼的合成：将水杨酸甲酯(33 mL)和水合肼(21 mL)加入溶剂无水乙醇(60mL)中，于75℃下回流12h，冷却析出得到2-羟基苯甲酰肼；过滤，用乙醇洗涤，备用。
OH-Ph-Cl的合成：将2-羟基苯甲酰肼(0.2 mol)和氯乙酰氯(0.22 mol)混合，以三乙胺为催化剂，以THF为溶剂，冰浴30min，然后在60℃下回流2h，得到OH-Ph-Cl。
双酰肼紫精衍生物L的合成：在圆底烧瓶中加入OH-Ph-Cl (0.039 mmol)和MeCN(20mL)，然后滴加4,4’-联吡啶(0.083 mmol)的MeCN (20mL)溶液，加入少量KI和18-冠醚-6，滴毕，于90℃回流48h。冷却，抽滤，残余物用MeCN和MeOH洗涤，得到紫色固体(为L的氯盐，L-Cl)；取以上紫色固体溶于H2O (20mL)得淡黄色透明溶液。加入NH4PF6 (为L-Cl的3倍当量)得淡黄色粉末。室温下搅拌12h。产物颜色在搅拌过程中由淡黄色变成蓝紫色。将该蓝紫色产物用水洗涤，使用该法得到L的六氟磷酸盐，为含水相粉末，并将其封存在H2O中。或将蓝紫色粉末溶解在H2O/MeCN (1:1 v/v)溶液中，置于60℃环境中24h，得到蓝紫色晶体即为L的含水相，并保存于水溶液中。
在DMSO-d6试剂中对产物进行氢谱核磁表征（见图1），对各组峰进行归属如下：11.66 ppm一个质子峰属于酚羟基上的H，11.21 -10.73ppm的质子峰属于肼基上的H，9.18-8.07 ppm的质子峰属于联吡啶基上的H，7.89-7.00 ppm的质子峰归属于苯环上的H，而5.68ppm的质子峰属于亚甲基上的H。
实施例2
L对环境湿度（RH）的检测：将L的含水相晶体置于滤纸上，放入湿度控制箱，调整空气湿度从RH=100%、82%、75%、60%、51%、43%、0%。取RH=100%与RH=0%的样品进行电子顺磁测试（ESR）与紫外可见漫反射（DRS）光谱测试。
产品功能性表征：
（1）利用X-射线单晶衍射确定L晶体结构，并利用ESR和DRS光谱测试该产品对RH的响应：
通过单晶结构来确认L的湿度感应与结合水的得失相关：当RH从100%降至60%再到0%的过程，L的颜色由蓝紫色变成灰绿色最后变为淡黄色。且当RH值在100-60%范围内变化时，该产品具有从蓝紫色到灰绿色的可逆颜色转变（图2中a）。我们利用单晶结构来验证晶体结构与湿度传感之间的构效关系。晶体结构（图2中b）中显示该产品具有5个结合水，并通过氢键网络束缚住彼此，正是由于水与水之间的束缚能力较弱，导致了L在一定RH条件下具有吸附脱附水的能力。该过程不仅能通过颜色加以分辨，还能通过DSC测试验证（图3）。同时L作为一类缺电子的紫精衍生物，对外加刺激具有一定的ESR以及颜色响应。我们通过了ESR光谱测试（图4），L发现在RH=100%时在g1=2.00623、g2=2.00344两处具有明显的自由基电子信号，该信号趋近自由基电子的g值（2.0023）；当RH=0%（样品在60℃下烘干）时，以上两处自由基信号明显减弱。我们还进行了DRS测试（图5），发现L在RH=100%时在500-700nm范围内具有强吸收峰，这归因于紫精自由基阳离子的生成。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (4)

1.一种双酰肼紫精衍生物，其特征在于：所述双酰肼紫精衍生物的结构式为：
。
2.根据权利要求1所述的双酰肼紫精衍生物的制备方法，其特征在于：以2-羟基苯甲酰肼、氯乙酰氯和4,4’-联吡啶为原料制备而成。
3.根据权利要求2所述的制备方法，其特征在于：包括以下步骤：将2-羟基苯甲酰肼和氯乙酰氯混合，以三乙胺为催化剂，以THF为溶剂，冰浴30min，然后在60℃下回流2h，加入4,4’-联吡啶，以KI和18-冠醚-6为催化剂，以乙腈为溶剂，90℃加热回流反应后，除去溶剂，用乙腈和甲醇洗涤粗产物；将粗产物溶于水中，加入过量的NH4PF6进行阴离子交换，搅拌片刻后得到蓝紫色晶体，为双酰肼紫精衍生物的含水相，将上述晶体干燥得到淡黄色晶体，为双酰肼紫精衍生物的无水相。
4.如权利要求1所述的双酰肼紫精衍生物在制备湿度传感材料中的应用。
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CN110105336A (zh) * 2019-05-30 2019-08-09 华南理工大学 紫精衍生物电致变色材料及其制备方法
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CN110526861A (zh) * 2018-05-09 2019-12-03 中国科学技术大学 紫精衍生物、其制备方法与电致变色器件
CN110105336A (zh) * 2019-05-30 2019-08-09 华南理工大学 紫精衍生物电致变色材料及其制备方法
CN111793062A (zh) * 2020-07-30 2020-10-20 南京邮电大学 一类新型非对称紫精化合物及其制备方法与应用

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