【摘要】：近年來,配位聚合物由于新穎多變的拓?fù)浣Y(jié)構(gòu)及在氣體吸附、發(fā)光性能、磁性及催化性能等領(lǐng)域的潛在應(yīng)用成為無機(jī)化學(xué)及有機(jī)化學(xué)研究的重要方向之一。含四個氮原子的四唑配體具有多樣的配位模式和化學(xué)性質(zhì),是構(gòu)筑具有獨特結(jié)構(gòu)和性能配合物的一類重要配體。配合物的構(gòu)建方法多種多樣,水熱合成法是構(gòu)筑配合物的重要方法之一,其中水熱原位反應(yīng)為配位化學(xué)和有機(jī)化學(xué)的結(jié)合建立了一種新的橋梁,因此越來越多的配位化學(xué)工作者致力于水熱或溶劑熱的原位反應(yīng)。本論文以4-(1H-四唑-5-基)苯酚(H2L~4)、3-(1H-四唑-5-基)苯酚(H2L~5)和2-(1H-四唑-5-基)苯酚(H2L~6)三個有機(jī)化合物為配體或者前驅(qū)配體,利用水熱法及溶劑揮發(fā)等方法設(shè)計合成了十五個新的過渡金屬配合物,通過紅外、X-射線單晶衍射、X-射線粉末衍射測試(PXRD)、熱重(TGA)等測試手段對十五個新的配合物進(jìn)行了結(jié)構(gòu)表征。同時,也深入研究了部分配合物的固態(tài)熒光性能、半導(dǎo)體性質(zhì)和磁性。具體研究內(nèi)容如下:1、合成了三個不同的四唑基酚衍生物:4-(1H-四唑-5-基)苯酚(H2L~4)、3-(1H-四唑-5-基)苯酚(H2L~5)和2-(1H-四唑-5-基)苯酚(H2L~6)配體,并對其進(jìn)行了表征。2、利用4-(1H-四唑-5-基)苯酚(H2L~4)、3-(1H-四唑-5-基)苯酚(H2L~5)、2-(1H-四唑-5-基)苯酚(H2L~6)和硝酸鹽在水熱條件下發(fā)生原位反應(yīng),得到了基于2,6-二硝基-4-(1H-四唑-5-基)苯酚(H2L1)、2,4,6-三硝基-3-(1H-四唑-5-基)苯酚(H2L2)和2,4-二硝基-6-(1H-四唑-5-基)苯酚(H2L3)配體的十個配合物:{[Zn_3(L~1)_2(OH)_2]·H_2O}_n(1)、[Ag_2(L~1)]_n(2)、[Co(HL~1)_2(H_2O)_4](3)、[Cu_3(L~1)_2(OH)_2(H_2O)]_n(4)、[Cu_7(HL~1)_2(L~1)_6(H_2O)_6]_n(5)、[Cu(L~1)(H_2O)_3]_n(6)、[Cu(HL~1)_2(H_2O)_4·2H_2O](7)、[Ag_2(L~2)]_n(8)、[Ag_8(L~3)_4(H_2O)]_n(9)和[Cu(L~3)(H_2O)_2]_n(10)。對配合物1-10進(jìn)行了一系列基本表征,結(jié)果表明配合物1、4和8為三維結(jié)構(gòu),2、5和9為二維結(jié)構(gòu),6和10為一維鏈結(jié)構(gòu),3和7為單核結(jié)構(gòu)。討論配體結(jié)構(gòu)和配位模式對配合物結(jié)構(gòu)的影響。深入研究了配合物1-3和8-9的固態(tài)熒光性能、配合物1-6和8-10的半導(dǎo)體性質(zhì)及配合物3-6和10的磁性。3、利用鄰羥基苯腈、NaN3分別與相應(yīng)的金屬鹽發(fā)生原位反應(yīng),得到了兩個鋅鎘配合物[Zn_3(L~6)_3(H_2O)]_n(12)和[Cd(L~6)(H_2O)]_n(13),用4-(1H-四唑-5-基)苯酚(H2L~4)和2-(1H-四唑-5-基)苯酚(H2L~6)配體在不同的條件下合成配合物[Ni_3(L~4)_3(H_2O)_(10)](11)、[Cd_2(HL~6)_4(H_2O)_4](14)和[Co(L6)(H_2O)]_n(15)。對配合物11-15的結(jié)構(gòu)進(jìn)行了測試表征,結(jié)果表明配合物11和14為單核結(jié)構(gòu),12、13和15為二維結(jié)構(gòu)。討論了配體的配位模式和金屬離子對其結(jié)構(gòu)的影響。并且研究了配體H2L~6和配合物12-14的固態(tài)熒光性能,配合物11-14的半導(dǎo)體性質(zhì),配合物11的磁性。
[Abstract]:In recent years, coordination polymers have become one of the important research fields in inorganic chemistry and organic chemistry due to their novel topological structure and potential applications in the fields of gas adsorption, luminescence, magnetic properties and catalytic properties. Tetrazolium ligands containing four nitrogen atoms have various coordination modes and chemical properties. They are important ligands with unique structure and properties. Hydrothermal synthesis is one of the most important methods for the construction of coordination compounds, in which hydrothermal in-situ reaction establishes a new bridge for the combination of coordination chemistry and organic chemistry. Therefore, more and more coordination chemists focus on in situ reactions of hydrothermal or solvothermal reactions. In this thesis, three organic compounds, 4- (1H-tetrazol-5-yl) phenol (H2L~4), 3- (1H-tetrazol-5-yl) phenol (H2L~5) and 2- (1H-tetrazol-5-yl) phenol (H2L~6), were used as ligands or precursor ligands. Fifteen new transition metal complexes were designed and synthesized by hydrothermal method and solvent volatilization method. The structures of 15 new complexes were characterized by infrared X-ray single crystal diffraction and X-ray powder diffraction (PXRD), thermogravimetric (TGA). At the same time, the solid state fluorescence properties, semiconductor properties and magnetic properties of some complexes were also studied. Three different tetrazolophenol derivatives: 4- (1H-tetrazol-5-yl) phenol (H2L~4) 3- (1H-tetrazol-5-yl) phenol (H2L~5) and 2- (1H-tetrazol-5-yl) phenol (H2L~6) ligands were synthesized. It was characterized by in situ reaction of 4- (1H-tetrazol-5-yl) phenol (H2L~4) 3- (1H-tetrazol-5-yl) phenol (H2L~5) -2- (1H-tetrazol-5-yl) phenol (H2L~6) with nitrate under hydrothermal conditions. 寰楀埌浜嗗熀浜，

本文編號：2176493