CN107936954B - 一种二维镉有机骨架配合物及其制备方法与应用 - Google Patents

一种二维镉有机骨架配合物及其制备方法与应用 Download PDF

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CN107936954B
CN107936954B CN201711199272.9A CN201711199272A CN107936954B CN 107936954 B CN107936954 B CN 107936954B CN 201711199272 A CN201711199272 A CN 201711199272A CN 107936954 B CN107936954 B CN 107936954B
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李芬芳
卢丽萍
朱苗力
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Abstract

本发明公开了一种二维镉有机骨架配合物及其制备方法和应用。所述配合物化学式为[Cd(μ5‑Hcbic)]n，其中H3cbic为1‑(4‑苯甲酰基)‑1H‑苯并咪唑‑5,6‑二羧酸。所述制备方法，是将摩尔比为1:2的H3cbic与氯化镉加入体积比为4:3的H2O和CH3CN中，室温搅拌30分钟后，在密闭反应釜中于160℃反应72小时，即得到无色块状晶体，产率为63％。本发明的配合物具有二维骨架结构，其中镉离子采用六配位的模式。在水溶液中，230nm波长的光激发下，Fe3+能使该配合物的荧光发生猝灭，该配合物可作为检测Fe3+的一种荧光探针。

Description

一种二维镉有机骨架配合物及其制备方法与应用
技术领域
本发明涉及过渡金属配合物，具体属于一种二维镉有机骨架配合物及其制备方法，以及该配合物在识别Fe3+中的应用。
背景技术
最近几年，由于一些金属离子和一些易挥发性的有机气体对人类和环境构成了严重的威胁，所以寻找一种有效的检测方法是最近人们研究的热点课题，其中Fe3+是人体必须的元素之一，在细胞中具有携带和运送氧的作用，但是过量的铁会造成细胞内的血色素沉积，引发肾衰竭、贫血、肝功能不全等疾病，因此，设计一种有效而又快速的检测Fe3+方法是十分重要的，其中荧光检测是一种灵敏度和选择性很高而且准确，经济实惠的一种检测方法，所以构筑一种荧光探针来检测Fe3+是一种很好的选择。
金属有机框架结构(MOFs)是一类由中心金属离子和有机配体自组装而成的配位聚合物，在气体吸附，光学，磁学等方面具有潜在的应用价值。1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸，由于含有三个羧基，可以通过全部脱质子或部分脱质子而与金属构筑多样的MOFs，同时裸露的氮原子可能会有识别金属的能力，可以作为识别金属离子的荧光探针，到目前为止，过渡金属与1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸构筑的配合物还未见报导。
发明内容
本发明的目的在于提供一种二维镉有机骨架配合物及其制备方法，以及该配合物在识别Fe3+中的应用。
本发明提供的一种二维镉有机骨架配合物，其化学式为：[Cd(μ5-Hcbic)]n，其中H3L为1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸；结构式为：
该配合物的晶体属于单斜晶系，空间群为P 21/c，晶胞参数： α＝γ＝90°，β＝101.05(3)°。该配合物中镉离子为六配位，每个Cd(II)离子与五个氧原子和一个氮原子配位，其中两个氧(O1,O4)来自同一配体HL2-中苯并咪唑上的两个羧基氧，另外三个氧(O1A,O2,O3,)分别来自三个配体HL2-的羧基氧，最后一个配位原子氮(N1)来自第五个配体HL2-，即该配合物是由金属与来自五个配体的氧原子结合形成的八面体结构，该配合物为二维层状结构。Cd-O键的键长范围为X射线粉末衍射证实晶体样品为均相。室温下，把16种不同的金属离子M(NO3)n(Mn+＝Li+,Na+,K+,Mg2+,Ca2+,Ba2+,Ag+,Cr3+,Fe2+,Zn2+,Ni2+,Co2+,Cu2+,Pb2+,Cu+和Fe3+)的水溶液与超声条件下配合物的水溶液按1:1体积混合，在230nm波长激发下，测不同混合物的荧光发射峰，结果表明当在配合物中加入Fe3+时，配合物的荧光发生了明显的猝灭，表明配合物[Cd(μ5-Hcbic)]n对Fe3+有很好的选择性。
本发明提供一种二维镉有机骨架配合物的制备方法，包括如下步骤：
(1)将摩尔比为1:2的1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸与CdCl2·2.5H2O加入到体积比为4:3的H2O和CH3CN混合溶剂中，置于聚四氟乙烯管中室温搅拌30分钟。
(2)将步骤(1)中的聚四氟乙烯管置于不锈钢反应釜中密封，温度控制在160℃，反应72小时，自然降温至室温，得到无色块状晶体，蒸馏水洗涤三次，真空干燥即可。
本发明的有益效果：
本发明的过渡金属镉有机骨架配合物通过混合溶剂热法合成得到，制备方法简单，成本低，产量高，晶相均一。
本发明提供的镉有机骨架配合物基于一种配体1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸构筑，室温条件下把不同的金属离子的水溶液与超声条件下配合物的水溶液按1:1体积混合，在230nm波长激发下，测不同混合物的荧光发射峰，结果发现Fe3+对配合物的荧光有猝灭作用，表明配合物[Cd(μ5-Hcbic)]n对Fe3+有很好的选择和识别性，可以用作识别Fe3+离子。
附图说明
图1本发明镉有机骨架配合物的结构图。
图2本发明镉有机骨架配合物在298K的X射线粉末衍射图(实验及模拟图)。
图3本发明镉有机骨架配合物的热分析曲线。
图4本发明镉有机骨架配合物及1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸在298K的荧光光谱图。
图5镉有机骨架配合物对金属离子的识别效果。
具体实施方式
实施例1.本发明配合物[Cd(μ5-Hcbic)]n的制备方法
称取0.05mmolH3cbic与0.1mmolCdCl2·2.5H2O放入10ml的聚四氟乙烯管中，并加入4ml H2O和3ml CH3CN，室温搅拌30分钟。然后将聚四氟乙烯管密封于不锈钢反应釜中，温度控制在160℃加热72小时，自然降至室温，得到无色块状晶体，用蒸馏水洗涤三次，真空干燥，所得镉配合物的产率为63％。元素分析：理论值：C 45.26,H 2.22,N6.21；实验值:C45.35,H 2.17,N 6.29。
实施例2.本发明配合物[Cd(μ5-Hcbic)]n的晶体结构
晶体结构测定采用北京同步辐射1W2B工作线站光源为入射辐射，MAR165CCD探测器，MARCCD和HKL2000程序收集并还原数据及晶胞参数，从差值Fourier电子密度图利用SHELXL-97直接法及最小二乘法修正得到各原子坐标，并经Lorentz和极化效应修正，最终解得晶体结构(图1)。C和O原子采用理论加氢。详细的晶体测定数据见表1。
表1配合物的晶体学数据
实施例3.本发明配合物[Cd(μ5-Hcbic)]n的物相分析
X射线粉末衍射如图2所示，实验衍射图谱与依据晶体结构模拟的粉末衍射图谱一致，表明晶体样品均一。
实施例4.本发明配合物[Cd(μ5-Hcbic)]n的热稳定性测试结果
热稳定性如图3所示，配合物在400℃左右配合物骨架开始逐渐坍塌。说明该配合物在室温至400℃范围可以稳定存在。
实施例5本发明配合物[Cd(μ5-Hcbic)]n的发光性质
在室温下测定了配体和配合物的固体荧光发射光谱(图4)。从图中可看出，在300nm波长激发下，配合物在408nm处有较强的蓝光发射峰，可以归因于电子在配体间的跃迁。与配体相比，配合物的荧光显著增强且发生了红移，原因是配体与金属离子配位后有效地增强了配体的刚性，降低了非辐射能量损失。
实施例6本发明配合物[Cd(μ5-Hcbic)]n对金属离子的识别性质
将2.3mg配合物加到40mL水中超声45分钟，静置，取上层清液备用。另取16种不同的金属离子M(NO3)n(Mn+＝Li+,Na+,K+,Mg2+,Ca2+,Ba2+,Ag+,Cr3+,Fe2+,Zn2+,Ni2+,Co2+,Cu2+,Pb2 +,Cu+和Fe3+)，配制成1.0×10-4M的水溶液，把不同的金属离子水溶液与配合物按1:1体积混合，在230nm波长激发下，测不同混合物的荧光发射峰，结果表明当在配合物中加入Fe3+时，配合物的荧光发生了明显的猝灭(图5),表明配合物[Cd(μ5-Hcbic)]n对Fe3+有很好的选择和识别性。

Claims (3)

1.一种二维镉有机骨架配合物，其特征在于，化学式为：[Cd(μ5-Hcbic)]n，其中H3cbic为1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸，结构式为：
该配合物的晶体属于单斜晶系，空间群为P 21/c，晶胞参数： α＝γ＝90°，β＝101.05(3)°。
2.如权利要求1所述的一种二维镉有机骨架配合物的制备方法，其特征在于，包括如下步骤：
(1)将摩尔比为1:2的1-(4-苯甲酰基)-1H-苯并咪唑-5,6-二羧酸与氯化镉加入到含有体积比为4:3的H2O和CH3CN混合溶剂的聚四氟乙烯管中,室温搅拌30分钟；
(2)将此聚四氟乙烯管置于不锈钢反应釜中密封，升温至160℃反应72小时，自然降至室温，得到无色块状晶体，用蒸馏水洗涤三次，真空干燥即可。
3.如权利要求1所述的一种二维镉有机骨架配合物在制备检测Fe3+的荧光探针中的应用。
CN201711199272.9A 2017-11-26 2017-11-26 一种二维镉有机骨架配合物及其制备方法与应用 Expired - Fee Related CN107936954B (zh)

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CN109879898B (zh) * 2019-04-12 2021-07-02 山西大学 一种二维双核镉配位聚合物及其制备方法和应用
CN111234252B (zh) * 2020-02-24 2021-08-27 重庆师范大学 一种镉-有机超分子荧光聚合物及其制法与应用
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