【摘要】：微孔材料化合物由于其豐富的化學(xué)結(jié)構(gòu)以及在催化、分離、離子交換、吸附及光學(xué)性質(zhì)等方面的潛在應(yīng)用引起了人們廣泛的研究。本論文通過調(diào)控反應(yīng)條件(溫度,壓強(qiáng),反應(yīng)時間等)、磷源(磷酸,亞磷酸,有機(jī)膦酸)、金屬離子以及作為結(jié)構(gòu)導(dǎo)向劑的有機(jī)胺,通過在水熱合成的方法,實現(xiàn)微孔金屬磷(膦)酸鹽化合物的多樣化自組裝。結(jié)合單晶X-射線衍射、紅外光譜分析、熱重、元素分析、熒光光譜、質(zhì)子導(dǎo)電、磁性等性質(zhì)研究對合成的晶體表征。論文具體工作如下:一、在水熱合成的條件下,選取磷酸為主體,在水-甲醇溶劑中,引入不同類型的含N雜環(huán)有機(jī)胺作為配體,實現(xiàn)了原位甲基化轉(zhuǎn)化。合成了三例通過原位生成模板劑(N,N,N’,N’-4-甲基哌嗪,N,N,-二甲基-1,4-二氮雜環(huán)[2,2,2])誘導(dǎo)下的新型金屬磷酸鋁化合物:[dmdabco][Al_2(HPO_4)_4](3-1)、[tmpip]_(0.5)[Al(HPO_4)_2](3-2)、[tmpip][Al_6(PO_4)_6(HPO_4)]?(H_2O)(3-3)。其中,化合物3-1和3-2是兩例同構(gòu)的,具有一維鏈結(jié)構(gòu)的金屬磷酸鋁化合物;化合物3-3是一例少見的P/Al比為6/7的三維開放骨架結(jié)構(gòu)化合物,其結(jié)構(gòu)由AlO_4,AlO_5,PO_4和HPO_4四面體單元構(gòu)成。二、在水熱合成條件下,選取亞磷酸為主體,在不同有機(jī)胺模板劑的誘導(dǎo)下合成三例具有新穎結(jié)構(gòu)的亞磷酸鋅化合物:[Hapy]_2[Zn_3(HPO_3)_4](3-4)[H_2hepip][Zn_3(HPO_3)_4](H_2O)_(0.25)(3-5)[H_2tmdab][Zn_3(HPO_3)_4](3-6)。三例化合物均由3-連接的HPO_3和4-連接的ZnO_4共頂點形成含有12-元環(huán)的亞磷酸鋅三維結(jié)構(gòu)化合物,其中,化合物3-6結(jié)構(gòu)中含有左右手螺旋鏈。三、在水熱合成條件下,以有機(jī)膦(羥基乙叉二膦酸或氨基三亞甲基磷酸)為主體,引入剛性的環(huán)狀有機(jī)胺,得到三例結(jié)構(gòu)新穎的過渡金屬有機(jī)膦酸鹽:[Zn_3{N(CH_2 PO3)3}(TIB)]·8H_2O(4-1),[Co3{N(CH_2 PO3)3}(TIB)]·9H_2O(4-2),[H_3TPT][Zn_3CH_3C(O)(PO3)2)]CH_3C(O)(PO3)2H)]·(H_2O)(4-3)。其中,化合物4-1和4-2是兩例同構(gòu)的、具有三維層-柱結(jié)構(gòu),層與層之間由有機(jī)配體作為柱撐結(jié)構(gòu),分別具有熒光性質(zhì)及磁性;化合物4-3是一例由金屬離子與有機(jī)膦配位構(gòu)成的二維層狀結(jié)構(gòu)化合物,值得注意的是該化合物具有光致/熱致可逆變色性質(zhì)。
[Abstract]:Due to their rich chemical structure and potential applications in catalysis, separation, ion exchange, adsorption and optical properties, microporous materials have been widely studied. In this paper, by regulating reaction conditions (temperature, pressure, reaction time, etc.), phosphorous sources (phosphoric acid, phosphorous acid, organic phosphonic acid), metal ions and organic amines as structural guidance agents, the method of hydrothermal synthesis was used. The multiplex self-assembly of microporous phosphorus (phosphine) acid compounds was realized. The synthesized crystals were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, fluorescence spectroscopy, proton conduction and magnetic properties. The main work of this paper is as follows: firstly, under the condition of hydrothermal synthesis, phosphoric acid was selected as the main body, and different kinds of heterocyclic organic amines containing N were introduced as ligands in water-methanol solvent to realize in situ methylation conversion. Three new metal aluminophosphate compounds induced by in situ formation of template (NNN, N, N, N, O, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N Compounds 3-1 and 3-2 are two isomorphic metal aluminophosphate compounds with one-dimensional chain structure, and compound 3-3 is a rare three-dimension open skeleton structure compound with P/Al ratio of 6 / 7. The structure of compound 3-2 is composed of AlOSP _ 4O _ 5O _ 5PO _ 4 and HPO_4 tetrahedron unit. Secondly, three novel zinc phosphite compounds with novel structure were synthesized by hydrothermal synthesis with phosphorous acid as the main body and induced by different organic amine templates: [Hapy] 2 [Zn_3 (HPO_3) 4] (3-4) [H_2hepip] [Zn_3 (HPO_3) 4] (H _ 2O) _ (0.25) (3-5) [H_2tmdab] [Zn_3 (HPO_3) _ 4] (3-6). In the three cases, the 3-linked HPO_3 and the 4-connected ZnO_4 co-apex to form the three-dimensional structure compound of zinc phosphite containing 12-member ring. The structure of compound 3-6 contains the left and right hand helical chain. 涓，

本文編號：2197647