【摘要】：微孔材料化合物由于其豐富的化學組成以及在催化、氣體儲藏、吸附、分離等方面的潛在應用引起了人們極大的研究興趣。本論文通過直接選取不同有機胺作為配體或采用模板劑的“原位”設計與合成策略,在水熱條件下實現(xiàn)微孔金屬(亞)磷酸鹽化合物的多樣化組裝。通過單晶X-射線衍射、元素分析、紅外光譜、粉末X-射線衍射、熱重、熒光等對合成晶體化合物進行結構表征與性質測試。論文具體工作如下:1、在水熱條件下,選取不同類型的柔性鏈狀有機胺、含N雜環(huán)有機胺作為配體,合成了四例新型的有機-無機雜化(亞)磷酸鋅化合物:[C6N2O2H16][Zn(HPO3)]2(3-1)、(NH4)[Zn5(PO4)3(HPO4)2(HAPIM)2]·(H2O)(3-2)、[Hampy][Zn2(HPO3)(PO4)](3-3)、[ampy][Zn2(HPO3)](3-4)。其中,化合物3-1是一例以柔性線型有機配體作為柱撐結構的有機-無機雜化亞磷酸鋅化合物;化合物3-2、3-3、3-4是以含N雜環(huán)有機胺作為配體合成的�；衔�3-2是一例含16-元環(huán)超大孔道結構的磷酸鋅化合物;化合物3-3是一例具有二維層結構的磷酸-亞磷酸鋅化合物,且具有熒光及光致變色性質;化合物3-2和化合物3-3的合成中,有機胺不僅作為配體參與了骨架的構建,而且還起到了結構導向劑的作用;化合物3-4的空間結構是由中性亞磷酸鋅層通過剛性含N雜環(huán)有機配體柱撐而成。2、水熱條件下,在水-甲醇介質中,實現(xiàn)了系列脂肪族有機胺及芳香族有機胺的原位甲基化轉化,包含1,4-二氮雜環(huán)[2,2,2]辛烷、哌嗪、1,4-二甲基哌嗪、2,6-二甲基哌嗪、3-氨甲基吡啶、吡啶、4,4’-聯(lián)吡啶;并分別在原位生成模板劑N,N’-二甲基-1,4二氮雜環(huán)[2,2,2]辛烷、N,N,N’,N’-四甲基哌嗪、N-甲基-2,6-二甲基哌嗪、N-甲基吡啶、N,N’-二甲基-4,4’-聯(lián)吡啶的誘導下合成了14例新穎金屬(亞)磷酸鹽化合物,包括四例不同維數(shù)的磷酸鈹化合物(化合物4-1~4-4),四例磷酸鎵化合物(化合物4-5~4-8),三例不同結構特點的磷酸鋅化合物(化合物4-9~4-11)以及三例亞磷酸鋅化合物(化合物4-12~4-14)。
[Abstract]:Due to their rich chemical composition and potential applications in catalysis, gas storage, adsorption and separation, microporous materials have attracted much attention. In this paper, by selecting different organic amines as ligands or adopting "in situ" design and synthesis strategy of template, we can realize the diversified assembly of microporous metal (hypophosphite) compounds under hydrothermal conditions. The structure and properties of the synthesized crystal compounds were characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction, thermogravimetry and fluorescence. In this paper, four novel organic-inorganic hybrid (C6N2O2H16) zinc phosphate compounds, [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4) were synthesized by using different types of flexible chain organic amines and N heterocyclic organic amines as ligands under hydrothermal conditions as follows: [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4). Compound 3-1 is an organic-inorganic hybrid zinc phosphite compound with flexible linear organic ligands as pillared structure, and compound 3-2C3-3Phosphite 3-4 is synthesized from N-containing heterocyclic organic amines as ligands. Compound 3-2 is a zinc phosphate compound with a large pore structure of 16-unit ring, compound 3-3 is a two-dimension structure of zinc phosphate-phosphite compound, and it has fluorescence and photochromic properties. In the synthesis of compound 3-2 and compound 3-3, organic amines not only participate in the construction of framework as ligands, but also act as structural guidance agents. The spatial structure of compound 3-4 is composed of neutral zinc phosphite layer supported by rigid heterocyclic organic ligands containing N. The in situ methylation of aliphatic organic amines and aromatic organic amines is realized in aqueous and methanol medium under hydrothermal conditions. It contains 1: 4- diaza-heterocyclic [2o _ 2o _ 2] octane, piperazine (1-dimethylpiperazine), 2-dimethyl-piperazine (2-dimethylpiperazine), 3-aminomethylpyridine (3-aminomethylpyridine), 4zapyridine, bipyridine; The synthesis of 14 cases of pyridine was carried out under the induction of in situ synthesis of the template agent NHN, dimethyl, diazocyclic [2, 2, n, 2] octanohexane, N, N-, tetramethyl, piperazine, N-, methyl-2, dimethyl, piperazine, and dimethylpyridine, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, Novel Metallic (sulfite) Phosphate compounds, It consists of four beryllium phosphate compounds (compounds 4-1n 4-4), four gallium phosphate compounds (compounds 4-54-8), three zinc phosphate compounds with different structural characteristics (compound 4-9nc-11) and three zinc phosphite compounds (compound 4-124-14).
【學位授予單位】：青島大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.4;O611.4

【共引文獻】

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1 李欣潔;含硼離子液體的合成、表征及其在硼磷酸鹽合成中的應用[D];東北大學;2012年

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本文編號：2141812