【摘要】：本論文采用水熱合成法,在不同有機(jī)羧酸配體調(diào)控下,分別將K8Na2[A-α-GeW9O34]·25H_2O和Na9[B-α-SbW9O33]·19.5H_2O前驅(qū)體與過渡金屬離子,鑭系金屬離子反應(yīng),通過調(diào)節(jié)體系的pH值、反應(yīng)時間、反應(yīng)溫度以及反應(yīng)物配比等條件,合成了二十例異金屬雜多鎢酸鹽,并通過元素分析,X-射線單晶衍射、紅外光譜、熱失重分析等手段對其結(jié)構(gòu)進(jìn)行表征。通過向反應(yīng)體系中引入不同羧酸配體(從單羧酸到多羧酸),我們合成了具有不同結(jié)構(gòu)的異金屬雜多鎢酸鹽,說明有機(jī)羧酸配體對構(gòu)筑不同結(jié)構(gòu)的異金屬雜多鎢酸鹽起到指導(dǎo)和調(diào)控作用,同時在多維框架結(jié)構(gòu)組裝的過程中起到結(jié)構(gòu)導(dǎo)向作用。此外,我們對相關(guān)化合物的熒光性質(zhì)進(jìn)行了研究,本文主要從以下四個部分進(jìn)行闡述：第一部分主要通過文獻(xiàn)調(diào)研,概述了3d-4f異金屬雜多鎢酸鹽的發(fā)展?fàn)顩r。第二部分通過采用水熱合成方法合成了六例通過醋酸橋聯(lián)兩個單核稀土取代的Keggin型3d-4f異金屬鍺鎢酸鹽：[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前驅(qū)體與Cu2+,Ln3+離子在有機(jī)配體存在的條件下合成的。化合物1-6是同構(gòu)的,為孤立結(jié)構(gòu),其基本骨架是由兩個單核稀土取代的單缺位Keggin型鍺鎢酸鹽單元通過兩個醋酸根配體連接形成夾心型二聚體,六個[Cu(en)2]2+陽離子分別與兩個Keggin型鍺鎢酸鹽單元相連。對化合物3和前驅(qū)體K8Na2[A-a-GeW9O34]·25H_2O的固態(tài)熒光性質(zhì)進(jìn)行了研究,結(jié)果表明化合物3主要顯示了Eu3+離子的特征發(fā)射,且鍺鎢酸鹽在熒光發(fā)射過程中存在貢獻(xiàn)。第三部分利用水熱合成方法,以Na9[B-a-SbW9O33]·19.5H_2O為前驅(qū)體,并向體系中引入鐵離子,稀土離子以及單羧基芳香配體,成功合成了五例新穎的具有三維拓展結(jié)構(gòu)的3d-4f異金屬銻鎢酸鹽：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為同構(gòu)化合物,代表了首例羧酸功能化的、具有三維拓展框架的FeⅢ-LnⅢ異金屬銻鎢酸鹽。它們的基本結(jié)構(gòu)單元都包含一個有機(jī)-無機(jī)雜化的[Fe_4(H_2O)_2(pic)_4(SbW_9O_(33))_2]10陰離子片段。該陰離子片段是由{Fe_4(H_2O)_2(pic)_4}夾心帶連接兩個三缺位的[SbW9O33]9單元形成的,并進(jìn)一步通過Fe3+離子上的有機(jī)配體與相鄰結(jié)構(gòu)單元上的稀土離子相連形成新穎的三維拓展結(jié)構(gòu)。從拓?fù)鋵W(xué)的角度講,該化合物為3,6-雙節(jié)點(diǎn)連接的(4·62)2(42·610·83)三維拓展結(jié)構(gòu)。我們對化合物10,11和前驅(qū)體Na9[B-α-SbW9O33]·19.5H_2O的熒光性質(zhì)進(jìn)行了研究。通過對比前驅(qū)體Na9[B-α-SbW9O33]·19.5H_2O在相同條件下的熒光壽命發(fā)現(xiàn)：三種化合物的熒光發(fā)射行為是由Na9[B-α-SbW9O33]·19.5H_2O和稀土元素共同作用的結(jié)果。第四部分利用水熱合成方法,向含有Na9[B-α-SbW9O33]·19.5H_2O前驅(qū)體、鐵離子和稀土離子的體系中引入雙羧基的吡啶-2,5-二甲酸配體,成功得到了兩類具有三維拓展結(jié)構(gòu)的銻鎢酸鹽：[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均包含一個羧酸配體取代的四鐵夾心的Krebs型銻鎢酸鹽的二聚單元,并在羧酸配體與稀土離子的連接下形成新穎的三維拓展結(jié)構(gòu)�；衔�12-13中兩個吡啶-2,5-二甲酸取代Krebs結(jié)構(gòu)銻鎢酸鹽的二聚單元夾心帶上八個水分子,并與兩個[Ln(H_2O)7]3+配離子相連,這種現(xiàn)象在Krebs多金屬氧酸鹽衍生物中是首次發(fā)現(xiàn)的。而14-20中Krebs結(jié)構(gòu)銻鎢酸鹽的二聚單元夾心帶上的十個水分子完全被配體取代,這在Krebs型多金屬氧酸鹽中也是首次發(fā)現(xiàn)的。同時進(jìn)一步說明了Krebs型多金屬氧酸鹽夾心帶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型兩種不同半徑的孔道結(jié)構(gòu),每個A型孔道周圍圍繞六個B型孔道這樣的結(jié)構(gòu)在3d-4f異金屬銻鎢酸鹽中屬首次發(fā)現(xiàn)。從拓?fù)鋵W(xué)的角度講,12-13表現(xiàn)出三維(53)2(54·62)2(56·64·72·93)網(wǎng)狀拓?fù)浣Y(jié)構(gòu),14-20表現(xiàn)出三維(4·62)2(42·610·83)網(wǎng)狀拓?fù)浣Y(jié)構(gòu)。化合物12-13與14-20是在同樣的合成條件得到的兩種不同結(jié)構(gòu)類型的化合物由此可見稀土離子的半徑對化合物結(jié)構(gòu)的形成具有重要作用。對14、15、17、18的熒光性質(zhì)進(jìn)行了研究,都顯示出鑭系離子的特征發(fā)射。對18的磁性進(jìn)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)(偽-GeW_(11)O_(39))]_(28)H_2O(3),[Cu(en)_2(H_2O)]_6[Gd(H_2O)(CH_3COO)(偽-GeW_(11)O_(39))]_(28)H_2O(4),[Cu(en)_2(H_2O)]_6[Dy(H_2O)(CH_3COO)(偽-GeW_(11)O_(39))]_(28)H_2O(5),[Cu(en)_2(H_2O)]_6[Ho(H_2O)(CH_3COO)(偽-GeW_(11)O_(39))]_(28)H_2O(6).鍖栧悎鐗，

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