羧酸调控的Keggin型3d-4f异金属杂多钨酸盐的合成、结构及性质研究
发布时间：2018-08-27 15:49
【摘要】：本论文采用水热合成法,在不同有机羧酸配体调控下,分别将K8Na2[A-α-GeW9O34]·25H_2O和Na9[B-α-SbW9O33]·19.5H_2O前驱体与过渡金属离子,镧系金属离子反应,通过调节体系的pH值、反应时间、反应温度以及反应物配比等条件,合成了二十例异金属杂多钨酸盐,并通过元素分析,X-射线单晶衍射、红外光谱、热失重分析等手段对其结构进行表征。通过向反应体系中引入不同羧酸配体(从单羧酸到多羧酸),我们合成了具有不同结构的异金属杂多钨酸盐,说明有机羧酸配体对构筑不同结构的异金属杂多钨酸盐起到指导和调控作用,同时在多维框架结构组装的过程中起到结构导向作用。此外,我们对相关化合物的荧光性质进行了研究,本文主要从以下四个部分进行阐述：第一部分主要通过文献调研,概述了3d-4f异金属杂多钨酸盐的发展状况。第二部分通过采用水热合成方法合成了六例通过醋酸桥联两个单核稀土取代的Keggin型3d-4f异金属锗钨酸盐：[Cu(en)_2(H_2O)]_6[Nd(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(1),[Cu(en)_2(H_2O)]_6[Sm(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(2),[Cu(en)_2(H_2O)]_6[Eu(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(3),[Cu(en)_2(H_2O)]_6[Gd(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(4),[Cu(en)_2(H_2O)]_6[Dy(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(5),[Cu(en)_2(H_2O)]_6[Ho(H_2O)(CH_3COO)(α-GeW_(11)O_(39))]_(28)H_2O(6)。化合物1-6是利用[A-a-GeW9O34]10前驱体与Cu2+,Ln3+离子在有机配体存在的条件下合成的。化合物1-6是同构的,为孤立结构,其基本骨架是由两个单核稀土取代的单缺位Keggin型锗钨酸盐单元通过两个醋酸根配体连接形成夹心型二聚体,六个[Cu(en)2]2+阳离子分别与两个Keggin型锗钨酸盐单元相连。对化合物3和前驱体K8Na2[A-a-GeW9O34]·25H_2O的固态荧光性质进行了研究,结果表明化合物3主要显示了Eu3+离子的特征发射,且锗钨酸盐在荧光发射过程中存在贡献。第三部分利用水热合成方法,以Na9[B-a-SbW9O33]·19.5H_2O为前驱体,并向体系中引入铁离子,稀土离子以及单羧基芳香配体,成功合成了五例新颖的具有三维拓展结构的3d-4f异金属锑钨酸盐：Na4[La(H_2O)_5]_2[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]·40H_2O(7), Na4[Pr(H_2O)_5]_2[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]·40H_2O(8), Na4[Nd(H_2O)_5]_2[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]·40H_2O(9), Na4[Sm(H_2O)_5]_2[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]·40H_2O(10), Na4[Eu(H_2O)_5]_2[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]·40H_2O(11),化合物7-11为同构化合物,代表了首例羧酸功能化的、具有三维拓展框架的FeⅢ-LnⅢ异金属锑钨酸盐。它们的基本结构单元都包含一个有机-无机杂化的[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]10阴离子片段。该阴离子片段是由{Fe_4(H_2O)_2(pic)_4}夹心带连接两个三缺位的[SbW9O33]9单元形成的,并进一步通过Fe3+离子上的有机配体与相邻结构单元上的稀土离子相连形成新颖的三维拓展结构。从拓扑学的角度讲,该化合物为3,6-双节点连接的(4·62)2(42·610·83)三维拓展结构。我们对化合物10,11和前驱体Na9[B-α-SbW9O33]·19.5H_2O的荧光性质进行了研究。通过对比前驱体Na9[B-α-SbW9O33]·19.5H_2O在相同条件下的荧光寿命发现：三种化合物的荧光发射行为是由Na9[B-α-SbW9O33]·19.5H_2O和稀土元素共同作用的结果。第四部分利用水热合成方法,向含有Na9[B-α-SbW9O33]·19.5H_2O前驱体、铁离子和稀土离子的体系中引入双羧基的吡啶-2,5-二甲酸配体,成功得到了两类具有三维拓展结构的锑钨酸盐：[Pr(H_2O)4(pdc)]2[Pr(H_2O)7]2[Fe_4(H_2O2)(pdc)2(SbW_9O_(33))_2]·18H_2O(12)[Nd(H_2O)4(pdc)]2[Nd(H_2O)7])2[Fe(H_2O2)2(pdc)2(SbW_9O_(33))_2]·18H_2O(12),2O)2(pdc)2(SbW_9O_(33))_2]·18H_2O(13),[Sm(H_2O)_6]_2[F24(H_2pdc)_4(SbW_9O_(33))_2]·49H_2O(14),[Eu(H_2O)_6]_2[F24(H_2pdc)_4(SbW_9O_(33))_2]·49H_2O(15),[Cd(H_2O)_6]_2[F24(H_2pdc)_4(SbW_9O_(33))_2]·49.33H_2O(16)[Tb(H_2O)_6]_2[Fe_4(H_2pdc)_4(SbW_9O_(33))_2]·49.33H_2O(17),[Dy(H_2O)_6]_2[Fe_4(H_2pdc)_4(SbW_9O_(33))_2]·49.33H_2O(18),[Ho(H_2O)_6]_2[Fe_4(H_2pdc)_4(SbW_9O_(33))_2]·49.33H_2O(19),[Er(H_2O)_6]_2[Fe_4(H_2pdc)_4(SbW_9O_(33))_2]·49.33H_2O(20),化合物12-20均包含一个羧酸配体取代的四铁夹心的Krebs型锑钨酸盐的二聚单元,并在羧酸配体与稀土离子的连接下形成新颖的三维拓展结构。化合物12-13中两个吡啶-2,5-二甲酸取代Krebs结构锑钨酸盐的二聚单元夹心带上八个水分子,并与两个[Ln(H_2O)7]3+配离子相连,这种现象在Krebs多金属氧酸盐衍生物中是首次发现的。而14-20中Krebs结构锑钨酸盐的二聚单元夹心带上的十个水分子完全被配体取代,这在Krebs型多金属氧酸盐中也是首次发现的。同时进一步说明了Krebs型多金属氧酸盐夹心带中配位水是有活性的。值得一提的是,化合物14-20中包含A型、B型两种不同半径的孔道结构,每个A型孔道周围围绕六个B型孔道这样的结构在3d-4f异金属锑钨酸盐中属首次发现。从拓扑学的角度讲,12-13表现出三维(53)2(54·62)2(56·64·72·93)网状拓扑结构,14-20表现出三维(4·62)2(42·610·83)网状拓扑结构。化合物12-13与14-20是在同样的合成条件得到的两种不同结构类型的化合物由此可见稀土离子的半径对化合物结构的形成具有重要作用。对14、15、17、18的荧光性质进行了研究,都显示出镧系离子的特征发射。对18的磁性进行研究。
[Abstract]:Twenty gold isomers were synthesized by hydrothermal synthesis under the control of different organic carboxylic acid ligands. The precursors of K8Na2 [A-alpha-GeW9O34]. 25H_2O and Na9 [B-alpha-SbW9O33]. 19.5H_2O were reacted with transition metal ions and lanthanide metal ions respectively. Twenty gold isomers were synthesized by adjusting the pH value, reaction time, reaction temperature and the ratio of reactants. Heteropolytungstates were characterized by elemental analysis, X-ray single crystal diffraction, infrared spectroscopy and thermogravimetric analysis. By introducing different carboxylic acid ligands (from monocarboxylic acid to polycarboxylic acid), Heteropolytungstates with different structures were synthesized, which indicated that the organic carboxylic acid ligands had different structures. The structure Heteropolytungstates play a guiding and regulating role in the assembly of multi-dimensional frameworks. In addition, we have studied the fluorescence properties of related compounds. This paper mainly elaborates on the following four parts: The first part summarizes the 3d-4f Heteropolytungstates mainly through literature research. In the second part, six Keggin-type 3d-4f isometallic germanium tungstates were synthesized by hydrothermal synthesis method. Six Keggin-type 3d-4f isometallic germanium tungstatesubstituted by acetic acid bridged with two mononuclear rare earth substituted by acetic acid bridged with two mononuclear rare earth substituted Keggin-type: Cu (en) _2 (H_2O)] _6 [Nd (H_2O) (CH_3 COO) (CH_3 COO) (CH_11) O (39)] (28) H_2O (1), [Cu (en) _2 (H_2O)]_6 [Sm (H_2O (H_2O (H_2O) (CH_3COO)] (CH_6(c)] _(28)H_2O(2),[Cu(en)_2(H_2O)]_6[Eu(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(3),[Cu(en)_2(H_2O)]_6[Gd(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(4),[Cu(en)_2(H_2O)]_6[Dy(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(5),[Cu(en)_2(H_2O)]_6[Ho(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(6).鍖栧悎鐗，
本文编号：2207736
[Abstract]:Twenty gold isomers were synthesized by hydrothermal synthesis under the control of different organic carboxylic acid ligands. The precursors of K8Na2 [A-alpha-GeW9O34]. 25H_2O and Na9 [B-alpha-SbW9O33]. 19.5H_2O were reacted with transition metal ions and lanthanide metal ions respectively. Twenty gold isomers were synthesized by adjusting the pH value, reaction time, reaction temperature and the ratio of reactants. Heteropolytungstates were characterized by elemental analysis, X-ray single crystal diffraction, infrared spectroscopy and thermogravimetric analysis. By introducing different carboxylic acid ligands (from monocarboxylic acid to polycarboxylic acid), Heteropolytungstates with different structures were synthesized, which indicated that the organic carboxylic acid ligands had different structures. The structure Heteropolytungstates play a guiding and regulating role in the assembly of multi-dimensional frameworks. In addition, we have studied the fluorescence properties of related compounds. This paper mainly elaborates on the following four parts: The first part summarizes the 3d-4f Heteropolytungstates mainly through literature research. In the second part, six Keggin-type 3d-4f isometallic germanium tungstates were synthesized by hydrothermal synthesis method. Six Keggin-type 3d-4f isometallic germanium tungstatesubstituted by acetic acid bridged with two mononuclear rare earth substituted by acetic acid bridged with two mononuclear rare earth substituted Keggin-type: Cu (en) _2 (H_2O)] _6 [Nd (H_2O) (CH_3 COO) (CH_3 COO) (CH_11) O (39)] (28) H_2O (1), [Cu (en) _2 (H_2O)]_6 [Sm (H_2O (H_2O (H_2O) (CH_3COO)] (CH_6(c)] _(28)H_2O(2),[Cu(en)_2(H_2O)]_6[Eu(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(3),[Cu(en)_2(H_2O)]_6[Gd(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(4),[Cu(en)_2(H_2O)]_6[Dy(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(5),[Cu(en)_2(H_2O)]_6[Ho(H_2O)(CH_3COO)(伪-GeW_(11)O_(39))]_(28)H_2O(6).鍖栧悎鐗，
本文编号：2207736
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