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  • 學位論文

金屬亞磷酸鹽的合成、結構與性質之研究

Syntheses, Structures and Properties of Metal Phosphites

指導教授 : 王素蘭

摘要


本論文主要利用水熱法及綠色深共熔熔劑的離子熱法來合成12 個化合物。所有化合物的鑑定方式都是以單晶X 光繞射儀收集數據後進行結構解析,並以粉末X 光繞射圖譜比對理論圖譜確定樣品純度後,進行後續的性質測量。這些化合物依不同的金屬中心、不同骨架或光學等性質分為A, B, C 三個系統: 系統A 的主題是純三價釩亞磷酸鹽 (A1-A3),在合成上首度使用四價硫酸釩 搭配相同的有機模板:環狀有機胺cyclohexylamine 以生成純三價釩化合物。其 中A1 具有互相交錯的二維超大環16R 隧洞,溶劑可填充體積高達45%;而進入骨架結構的硼,在化合物失去部分配位水時,扮演了穩定結構的重要角色,因此可以使A1 單純透過脫水,來達到罕見的固態氧化還原性質。在A1 反應物中,額外導入ZnO 可得到A2 雙層(double layer)結構,是首度發現的鋅釩雙金屬亞磷酸鹽;另一方面以Ga2O3 取代ZnO 來反應,則可得到稀有的掌性結構A3。 系統B 包含了具非中心對稱結構與光學性質的六個化合物(B1-B6):B1 是純錫(II)亞磷酸鹽,具強的二次倍頻訊號,可自身放出白光;B2 是摻雜Mn2+的錫亞磷酸鹽,與B1 等結構,然較B1 具有更高的白光量子效率。B3 與B4 都具有中性的鋅亞磷酸草酸骨架,是兩個同分異構的多形體(polymorph),有Sn2+摻雜在其中,具特殊的一維階梯形薄板結構,雖二者結構相似度高,但放光卻大不相同。接著我們首度使用蔗糖做為起始反應物來導引出兩個超大環20R 鋅亞磷酸鹽結構B5 與B6,各為非中心對稱20R 與掌性20R 結構的首例。 在系統 C 中,使用不同長度的直碳鏈單胺,來得到三個化合物(C1-C3):C1是40R 雙金屬鎵鋅亞磷酸鹽,因摻雜了Mn2+而可自發性放出白光,且Mn2+的位置可被清楚定出;C2 則是鎵亞磷酸鹽mesolamellar 結構,有接近3 nm 的層間距; C3 可視為是C1 結構的擴張,將環數擴增至驚人的64R。系統C 的價值在於能利用特定形式的有機模板,來達成孔徑大小與結構連結的可預測性與可控制性。此外,具有如此大的層間距及環數,卻還能獲得單晶來解出結構更是前所未有的重要突破。 綜合以上,本論文在策略性的實驗設計下開發了三個系統,這些化合物不論是在結構上或性質上都能有創新的表現,且後續仍有很多值得繼續往深處挖掘的潛力存在。

並列摘要


12 compounds synthesized by hydrothermal and ionothermal methods were characterized by single crystal X-ray diffraction; their purity was examined by comparing powder diffraction patterns with theoretical patterns and their physical properties were also measured. These compounds are grouped into three systems based on different metal centers, frameworks or optical properties, namely System A, B and C. System A includes three vanadium(III) phosphites (A1-A3), which were synthesized for the first time by vanadium(IV) sulfate with the same organic template, i.e. the cyclic-type amine cyclohexylamine. A1 possesses intersecting 2D extra large 16R channels, with solvent accessible volume reaches up to 45%. Solid state redox property was achieved in A1 by losing and regaining coordinating water ligand and possibly contributed by the incorporated boron which plays an important role in stabilizing the structure. With zinc oxide (ZnO), a bimetal vanadium zincophosphite A2 was obtained, featured with a double layered structure. Furthermore, by replacing ZnO with gallium oxide, a rare chiral structure A3 was prepared. System B includes six non-centrosymmetric and optical compounds (B1-B6). B1 is a tin(II) phosphite with obvious second harmonic generation signal, with intrinsic white light emission. With identical structure with B1, B2 possesses higher white light quantum efficiency by doping manganese(II). B3 and B4 are polymorphs, both of which are neutral zinc oxalatophosphite structure. Even though both structures are strongly related, their optical properties are quite different. Without precedent, the use of sucrose as chiral induction reagent has been proved to be an effective route for synthesizing B5 and B6, two 20R non-centrosymmetric structures never revealed. System C includes three compounds (C1-C3), whose structures were all induced by aliphatic monoamines with different straight carbon-chain-length. The incorporation of manganese(II) in 40R gallium zincophosphite C1 contributed to intrinsic white light emission. The mesolamellar gallium phosphite C2 possesses almost 3 nm interlayer distance. C3 can be regarded as the structural expansion of C1, creating the channel size from 40R to amazing 64R. By using specific type of organic templates, the channel size and the structural connectivity can be well controlled and redicted. Besides, considering the meso-scale interlayer distance and pore size in C2 and C3, obtaining single crystals for structure characterization of both compounds was unprecedentedly achieved. In this research, three systems have been developed by strategic experiments, and both structures and properties of all compounds are creative and inspiring. More possibilities on these systems for continuing further investigation are promising in future.

並列關鍵字

無資料

參考文獻


[11] 國立清華大學碩士論文(2012),秦志遠,「具掌性骨架與超大隧洞結構之金屬亞磷酸鹽的合成與鑑定」。
[12] Lin, C. H.; Wang, S. L.; Lii, K. H. J. Am. Chem. Soc. 2001, 123, 4649−4650.
[7] Lin, C. H.; Wang, S. L.; Lii, K. H. J. Am. Chem. Soc. 2001, 123, 4649−4650.
[16] Lai, Y. L.; Lii, K. H.; Wang, S. L. J. Am. Chem. Soc. 2007, 129, 5350−5351.
[2] (a) Lin, C. H.; Wang, S. L.; Lii, K. H. J. Am. Chem. Soc. 2001, 123, 4649−4650; (b) Lai, Y. L.; Lii, K. H.; Wang, S. L. J. Am. Chem. Soc. 2007, 129, 5350−5351.

被引用紀錄


林新堯(2013)。具有新穎結晶性通道結構的含鋅金屬亞磷酸鹽的合成、鑑定與性質研究〔博士論文,國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-2511201311323559

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