CN106478563A - 一种基于2,5‑呋喃二羧酸的四核锌金属有机配合物及其制备方法 - Google Patents

一种基于2,5‑呋喃二羧酸的四核锌金属有机配合物及其制备方法 Download PDF

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CN106478563A
CN106478563A CN201610848064.6A CN201610848064A CN106478563A CN 106478563 A CN106478563 A CN 106478563A CN 201610848064 A CN201610848064 A CN 201610848064A CN 106478563 A CN106478563 A CN 106478563A
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dicarboxylic acid
furan dicarboxylic
zinc metal
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覃亮
郭海福
马德运
雷佳眉
黄漫菲
刘慧敏
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Zhaoqing Agile Graphic Printing Co Ltd
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Abstract

本发明涉及一种基于2,5‑呋喃二羧酸的四核锌金属有机配合物，该金属有机配合物是重复单元为[Zn4(FDC)4(H2O)11]的Zn(II)金属有机配合物，所述的化学式[Zn4(FDC)4(H2O)11]中的FDC为失去2个H的2,5‑呋喃二羧酸配体；本发明所述的四核锌金属有机配合物发射蓝色荧光，荧光寿命为112.3ns，可用于荧光材料的制备。

Description

一种基于2,5-呋喃二羧酸的四核锌金属有机配合物及其制备 方法
技术领域
本发明涉及金属有机配合物，具体涉及基于2,5-呋喃二羧酸的锌金属有机配合物及其制备方法。
背景技术
金属有机配合物是一种由金属离子与有机配体在一定条件下通过自组装合成的金属有机框架材料，具有孔隙率高、结构可塑、孔径大小均匀等特点。金属有机配合物作为一种新型功能材料，在荧光、磁性、吸附和载药等领域具有潜在的应用价值[1-4]。
含有共扼电子效应的有机配体与含有d10电子构型的Zn、Cd、Cu等金属结合的金属有机配合物一般都具有荧光效应，在制备新型发光材料方面具有重要的应用价值[5-6]。目前，具有荧光效应的基于2,5-呋喃二羧酸的四核锌金属有机配合物的报道比较少见。
参考文献：
[1]Song T,Yu J,Cui Y,et al.Encapsulation of dyes in metal–organicframeworks and their tunable nonlinear optical properties[J].DaltonTransactions,2016,45(10):4218-4223.
[2]Zhang W,Xiong R G.Ferroelectric metal–organic frameworks[J].Chemical reviews,2011,112(2):1163-1195.
[3]Ma D Y,Li Z,Xiao J X,et al.Hydrostable and nitryl/methyl-functionalized metal–organic framework for drug delivery and highly selectiveCO2adsorption[J].Inorganic chemistry,2015,54(14):6719-6726.
[4]Nazari M,Rubio‐Martinez M,Tobias G,et al.Metal‐Organic‐Framework‐Coated Optical Fibers as Light‐Triggered Drug Delivery Vehicles[J].AdvancedFunctional Materials,2016,26(19):3244-3249.
[5]Wu Y,Wang J,Zou L,et al.Luminescence sensing of an unusualtetranodal3-connected topology of Cu(I)-MOF[J].Inorganic ChemistryCommunications,2016,69:13-15.
[6]Formica M,Fusi V,Giorgi L,et al.New fluorescent chemosensors formetal ions insolution[J].Coordination Chemistry Reviews,2012,256(1):170-192.
发明内容
本发明的目的是提供一种基于2,5-呋喃二羧酸的四核锌金属有机配合物，该金属有机配合物发射蓝色荧光，可应用于荧光材料。
本发明解决上述问题的技术方案是：
一种基于2,5-呋喃二羧酸的四核锌金属有机配合物，该金属有机配合物是重复单元为[Zn4(FDC)4(H2O)11]的Zn(II)金属有机配合物，所述的化学式[Zn4(FDC)4(H2O)11]中的FDC为失去2个H的2,5-呋喃二羧酸配体；所述的四核锌金属有机配合物具有一维链状结构。该金属有机配合物属于单斜晶系，P21/c空间群，晶胞参数分别为a＝2.21533(8)nm，b＝0.73457(3)nm，c＝3.02012(8)nm，β＝132.972(2)°。红外光谱数据(KBr)为：3381(vs),3141(m),1570(vs),1475(w),1425(w),1371(vs),1222(w),1085(w),1017(m),967(m),794(s),622(w),522(w)cm-1。上述四核锌金属有机配合物在常温下为无色单晶，其重复结构单元含有4个Zn2+离子，4个FDC2-离子和11个配位水分子。金属中心Zn(II)为六配位结构，分别与来自FDC2-配体中的羧基氧原子和水中的氧原子形成畸变八面体构型。其中，四个Zn(II)(Zn1-Zn4)形成四核[Zn4(μ3-OOCchelating-bridging)4]线性结构单元，FDCA配体以μ2-螯合-桥连方式连接相邻两个Zn(II)形成无限的一维链状结构。
本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物是将2,5-呋喃二羧酸与Zn(NO3)2·6H2O混合后在溶剂热反应条件下得到。
本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物的制备方法包括以下步骤：
(1)将溶剂水和无水乙醇(分析纯)按照1:1(体积比)的比例混合均匀，得到混合溶剂；
(2)将等摩尔量的Zn(NO3)2·6H2O和FDCA加入到一定量的上述混合溶剂中，然后搅拌30分钟；
(3)将步骤2中物质加入到容积为23mL的聚四氟乙烯反应釜中，自生压力下保持130℃恒温反应72小时，然后按照一定的速率降至室温；
(4)将步骤3得到的产物过滤，收集晶体，并用无水乙醇洗涤后干燥，得到所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物。
本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物发射明亮的蓝色荧光，表现出良好的荧光特性，可应用于荧光材料。
本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物的其制备方法具有以下优点：反应条件温和，纯度高，无毒无害，做到了绿色化学，无需惰性气体保护；原料来源广泛，容易获得。
附图说明
图1为Zn2+的配位环境。
图2为FDCA配体的配位模式图。
图3为本发明所述基于的2,5-呋喃二羧酸的四核锌金属有机配合物的一维链状结构图。
图4为本发明所述基于2,5-呋喃二羧酸的四核锌金属有机配合物的三维固体荧光谱图。
具体实施方式
实施例1
1、基于2,5-呋喃二羧酸的四核锌金属有机配合物的制备
制备方法包括以下步骤：
(1)将溶剂水和无水乙醇(分析纯)按照1:1(体积比)的比例混合均匀，得到混合溶剂；
(2)将等摩尔量的Zn(NO3)2·6H2O(0.15g,0.5mmol)和FDCA(0.078g,0.5mmol)加入到12mL上述混合溶剂中，然后搅拌30分钟；
(3)将步骤2中物质加入到容积为23mL的聚四氟乙烯反应釜中，在自生压力下保持130℃恒温反应72小时，然后以5℃/h的速率降至室温；
(4)将步骤3中的混合物过滤，收集晶体，并用无水乙醇洗涤后干燥，获得无色晶体(根据FDC计算其产率：68％)。
2、基于2,5-呋喃二羧酸的四核锌金属有机配合物的鉴定
通过下述元素分析、IR光谱和X-射线单晶衍射分析鉴定，上述步骤1所得到的无色晶体为本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物，其重复单元的分子式为[Zn4(FDC)4(H2O)11]。
(1)元素分析C24H30O32Zn4：理论值：C,26.4；H,2.7；实验值：C,26.8；H,2.5。
(2)红外光谱(KBr pellet，cm-1)：3381(vs),3141(m),1570(vs),1475(w),1425(w),1371(vs),1222(w),1085(w),1017(m),967(m),794(s),622(w),522(w)。
(3)X-射线单晶衍射：晶体学参数和部分键长如表1和表2所示。X-射线单晶衍射结果表明，上述四核锌金属有机配合物中的重复单元为不对称单元，每个不对称结构单元中含有4个Zn2+离子，4个FDC2-离子和11个配位水分子。如图1所示，Zn1、Zn2和Zn4均为六配位结构，分别与两个FDC2-配体中的三个羧基氧原子(例如与Zn1相连的O4、O5、O9)与三个配位水分子中的氧原子(与Zn1相连的O6、O7、O8)连接成畸变八面体构型；Zn3与两个FDC2-配体中的三个羧基氧原子(O17、O18、O25)、两个配位水分子中的氧原子(O22、O24)以及一个独立氧原子(O23)连接形成畸变八面体构型。其中，四个金属中心Zn(II)形成四核[Zn4(μ3-OOCchelating-bridging)4]线性结构单元，FDCA配体以μ2-螯合-桥连方式(图2所示)配位，连接相邻两个Zn(II)形成无限的一维链状结构，配位水分子作为端基配体与Zn(II)金属中心相连(图3所示)。
表1.[Zn4(FDC)4(H2O)11]的晶体学参数
实验式 C24H30O32Zn4 Z 4
式重 1091.96 D(g·cm3) 2.017
温度(K) 296(2) 反射收集的/独特的 22778/5310
晶系 单斜晶系 Rint 0.0316
空间群 P21/c F(000) 2200
a(nm) 2.21533(8) μ/mm-1 2.756
b(nm) 0.73457(3) GOF 1.098
c(nm) 3.02012(8) R(I>2σ) R1＝0.0679
β(°) 132.972(2) R(所有数据) wR2＝0.2070
V(nm3) 3.5960(2)
R＝∑(‖Fo︱－︱Fc‖)/∑︱Fo︱.wR＝[∑w(Fo 2–Fc 2)2/∑w(Fo)2]1/2.
表2.[Zn4(FDC)4(H2O)11]的部分键长键角
对称Cudes：i＝1+x，0.5-y，0.5+z。
实施例2：四核锌金属有机配合物的荧光性能研究
本实施例采用实施例1得到的基于2,5-呋喃二羧酸的四核锌金属有机配合物进行荧光性能研究。具体研究方法如下所述：
(1)三维荧光性能测试：在室温下测量基于2,5-呋喃二羧酸的四核锌金属有机配合物在200-600nm范围内的三维固体荧光光谱。
(2)实验结果
三维固体荧光光谱结果显示(如图4)，本发明所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物发射明亮的蓝色荧光，在370nm激发波长下的最大荧光发射波长为465nm。

Claims (2)

1.一种基于2,5-呋喃二羧酸的四核锌金属有机配合物，其特征在于：所述金属有机配合物是重复单元为[Zn4(FDC)4(H2O)11]的Zn(II)金属有机配合物，所述的化学式[Zn4(FDC)4(H2O)11]中的FDC为失去2个H的2,5-呋喃二羧酸配体；所述的四核锌金属有机配合物具有一维链状结构。该金属有机配合物属于单斜晶系，P21/c空间群，晶胞参数分别为a＝2.21533(8)nm，b＝0.73457(3)nm，c＝3.02012(8)nm，β＝132.972(2)°。红外光谱数据(KBr)为：3381(vs),3141(m),1570(vs),1475(w),1425(w),1371(vs),1222(w),1085(w),1017(m),967(m),794(s),622(w),522(w)cm-1。
2.如权利要求1所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物的制备方法，其特征在于，所述方法包括以下步骤：
(1)将溶剂水和无水乙醇(分析纯)按照1:1(体积比)的比例混合均匀，得到混合溶剂；
(2)将等摩尔量的Zn(NO3)2·6H2O和FDCA加入到一定量的上述混合溶剂中，然后搅拌30分钟；
(3)将步骤2中物质加入到容积为23mL的聚四氟乙烯反应釜中，自生压力下保持130℃恒温反应72小时，然后按照一定的速率降至室温；
(4)将步骤3得到的产物过滤，收集晶体，并用无水乙醇洗涤后干燥，得到所述的基于2,5-呋喃二羧酸的四核锌金属有机配合物。
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CN107286185A (zh) * 2017-07-10 2017-10-24 肇庆学院 一种镉金属有机骨架材料及其制备方法
CN107286184A (zh) * 2017-07-10 2017-10-24 肇庆学院 一种锌金属有机骨架材料及其制备方法
CN108690055A (zh) * 2018-05-11 2018-10-23 苏州凌科特新材料有限公司 一种钡的配合物及其制备方法和应用
CN111116931A (zh) * 2019-12-31 2020-05-08 肇庆学院 一种基于2,5-呋喃二羧酸的Cd(Ⅱ)金属有机配合物及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107286185A (zh) * 2017-07-10 2017-10-24 肇庆学院 一种镉金属有机骨架材料及其制备方法
CN107286184A (zh) * 2017-07-10 2017-10-24 肇庆学院 一种锌金属有机骨架材料及其制备方法
CN107286184B (zh) * 2017-07-10 2019-05-28 肇庆学院 一种锌金属有机骨架材料及其制备方法
CN108690055A (zh) * 2018-05-11 2018-10-23 苏州凌科特新材料有限公司 一种钡的配合物及其制备方法和应用
CN111116931A (zh) * 2019-12-31 2020-05-08 肇庆学院 一种基于2,5-呋喃二羧酸的Cd(Ⅱ)金属有机配合物及其制备方法

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