CN111875624A - 一种基于bteb的四核锌配合物的制备、结构和荧光应用 - Google Patents

一种基于bteb的四核锌配合物的制备、结构和荧光应用 Download PDF

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CN111875624A
CN111875624A CN202010509391.5A CN202010509391A CN111875624A CN 111875624 A CN111875624 A CN 111875624A CN 202010509391 A CN202010509391 A CN 202010509391A CN 111875624 A CN111875624 A CN 111875624A
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bteb
zinc complex
tetranuclear
fluorescent
bridging
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CN111875624B (zh
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黎燕
张省媚
李恒仕
孙涛
叶萍
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Guilin University of Technology
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Abstract

本发明公开了一种基于bteb的四核锌配合物的制备、结构和荧光应用。本发明所述四核锌配合物的化学式为[Zn2(HCOO)2(μ2‑bteb)]2(μ2‑O)2，其中bteb为1,4‑双[(2,2':6',2”‑三联吡啶)‑4'‑基]苯有机桥联配体。每个五配位的ZnII金属中心位于ZnN3O2变型三角双锥几何构型中。bteb桥联两个五配位的ZnII金属中心形成双核单元。两个双核单元由两个桥联氧进一步桥联为矩形四核锌结构。将Zn(NO3)2·6H2O溶解于5mL水中，将上述溶液滴加入3mL含有bteb的二甲基甲酰胺溶液中。混合液转入20mL聚四氟乙烯内衬不锈钢高压釜中，在160℃下加热72h，冷却后得到上述锌配合物。合成的配合物具有较好的热稳定性，在275nm波长的紫外光激发下在395nm处有强发射。与自由bteb配体相比较，bteb与ZnII离子配位后发光红移。研究表明其在荧光材料领域可得以应用。

Description

一种基于bteb的四核锌配合物的制备、结构和荧光应用
技术领域
本发明属于配合物技术领域，具体涉及一种新型四核锌配合物的晶体结构及其制备和荧光应用。
背景技术
双三联吡啶因其分子内有共轭大π键，使得该配体具有很强的σ给电子和π受电子能力，空间位阻小，对各种金属离子尤其是过渡金属离子具有强结合能力。形成的配合物在分子导线，金属超分子组装体，发光系统、电致变色和化学传感器等方面都有潜在的所应用价值。由一个中心苯环连接两个三联吡啶基团的1,4-双[(2,2':6',2”-三联吡啶)-4'-基]苯(bteb)就是一种优良的双三联吡啶配体。其对金属中心具有很强的螯合能力，与金属离子配位配位模式多样。采用上述配体与过渡金属锌离子配合形成新型配合物以得到结构新颖性质多样的发光材料。
发明内容
本发明的目的：提供一种新型四核锌配合物的结构及其制备和荧光应用。
本发明的思路：采用bteb为桥联配体与硝酸锌通过溶剂热法获得荧光性四核锌配合物。
荧光性四核锌配合物的结构见附图1。本发明所述四核锌配合物的化学式为[Zn2(HCOO)2(μ2-bteb)]2(μ2-O)2，其中bteb为1,4-双[(2,2':6',2”-三联吡啶)-4'-基]苯有机桥联配体。该配合物属于三斜晶系，空间群为Pī，其晶胞参数为a＝10.8519(6)，b＝12.4620(6)，c＝14.4253(6)，α＝79.394(4)，β＝70.329(4)°，γ＝77.113(4)，V＝1778.04(16)。
上述四核锌配合物的荧光性质研究：
四核锌配合物的室温固态荧光光谱图见附图2。从图可以看出：Zn配合物，在274nm处激发时，最大发射出现在394nm处，与bteb自由配体相比，红移了大约20nm。研究表明其在荧光材料领域可得以应用。
上述四核锌配合物的制备方法：将Zn(NO3)2·6H2O溶解于5mL水中，将上述溶液滴加入3mL含有bteb的二甲基甲酰胺溶液中。混合液转入20mL聚四氟乙烯内衬不锈钢高压釜中，在160℃下加热72h，冷却后得到上述锌配合物。
附图说明
图1是本发明的bteb桥联的四核锌配合物分子结构图。
图2是本发明的bteb桥联的四核锌配合物室温固态荧光光谱图。
具体结构描述
每个五配位的ZnII金属中心位于ZnN3O2变型三角双锥配位几何构型中。每个配合物分子结构包含两个桥联bteb分子、两个桥联氧原子、四个单齿配位甲酸分子和四个ZnII离子。bteb配体桥联两个五配位的ZnII金属中心形成双核单元。两个双核单元由两个桥联氧进一步桥联为矩形四核锌结构。Zn1-N1、Zn1-N2和Zn1-N3的距离分别为2.089(2)、2.220(3)和
Figure BDA0002527679860000022
betb桥联的ZnII…ZnII距离为
Figure BDA0002527679860000023
而O桥联的ZnII…ZnII距离为
Figure BDA0002527679860000021

Claims (6)

1.一种荧光性四核锌配合物，其特征在于：所述四核锌配合物的化学式为：[Zn2(HCOO)2(μ2-bteb)]2(μ2-O)2，其中bteb为1,4-二[[2,2':6',2”-三联吡啶]-4'-基]苯。
2.根据权利要求1所述的荧光性四核锌配合物，其特征在于：属于三斜晶系，空间群为Pī，其晶胞参数为a＝10.8519(6)，b＝12.4620(6)，c＝14.4253(6)，α＝79.394(4)，β＝70.329(4)°，γ＝77.113(4)，V＝1778.04(16)。
3.权利要求1所述的荧光性四核锌配合物，其特征在于：每个五配位的ZnII金属中心位于ZnN3O2变型三角双锥几何构型中；配位几何构型中的三个氮原子分别来源于桥联bteb的一端三联吡啶，两个氧原子分别来源于一个单齿配位的甲酸分子和桥联氧原子；1,4-双[[2,2':6',2”-三联吡啶]-4'-基]苯有机桥联配体桥联两个五配位的ZnII金属中心形成双核结构单元；两个双核结构单元由两个桥联氧原子进一步桥联为矩形四核锌结构。
4.权利要求1所述的荧光性四核锌配合物的制备方法，其特征在于：将Zn2(NO3)2·6H2O溶解于5mL水中，将上述溶液滴加入3mL含有bteb的二甲基甲酰胺溶液中；混合液转入20mL聚四氟乙烯内衬不锈钢高压釜中，在160℃下加热72h，冷却后得到上述锌配合物。
5.权利要求1所述的四核锌配合物，其荧光性能特征在于：在274nm波长的紫外光激发下，在394nm处有强发射；与自由bteb配体相比较，bteb与ZnII离子配位后发光红移。
6.权利要求1所述的四核锌配合物的应用，其特征在于：发蓝紫光在荧光材料领域可得以应用。
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