The Designed Synthesis And Porperties Of New Types Of Metal-organic And Organic Porous Materials

Materials with regular porous structures are important in the areas of materialscience. The traditional porous materials have been widely used in many industrialprocesses such as catalysis, adsorption and separation, and ion exchange, etc., as wellas some in new application fields such as photoluminescence, magnetism, electronics,etc. Meanwhile, the development of new kinds of porous materials such as organicporous materials and metal–organic materials has been an indispensablecomplementary and alternative to the traditional porous materials in some applications.The research of porous materials has attracted considerable attentions in recentdecades. In the thesis, we focused on the research of organic porous materials andmetal–organic materials. With the help of topological knowledge, the organic porousmaterials and metal–organic materials with different properties are obtained throughdiverse synthesis strategies with the employment of novel ligands and organicmonomers.The main results in the thesis are summarized as follows:1With the help of several kinds of different organic synthesis methodology, aseries of luminescent porous organic materials (LMOPs) were successfullysynthesized. First, the Heck coupling reaction was used for the first time in thepreparation of organic porous materials and a novel class of luminescent microporousorganic polymers, namely, LMOP-1–3, has been constructed with1,3,5-tri(4-ethenylphenyl)benzene and aromatic halides. These materials can be usedas sensors in the detection of picric acid with their excellent photoluminescentproperties. Then, considering that potassium vinyltrifluoroborate (PVTFB) is a stable,commercial available and environmental benign solid, it was used for the first timehere in the preparation of LMOP-7–10through the palladium catalyzed tandemSuzuki–Heck C–C coupling reactions. The successful usage of such strategy hasavoided the synthesis of olefin intermediates for the Heck reactions. The materials obtained can be used for the sensitive detection of picric acid due to their excellentluminescent behaviors. At last, the commercial available octavinylsilsesquioxane wasused here for the synthesis of luminescent microporous organic–inorganic hybridpolymers (PS-1–4), these materials can also be used for the detection of picric aciddue to their luminescent features. Moreover, PS-1s polymerized in different timeswere synthesized for the energy transfer experiments with coumarin6.2. The cross-linked porous organic polymer, donated as Triph–SPhos, wassynthesized by the copolymerization of terphenyl with one kinds of organophosphoruscompound (2-Dicyclohexylphosphino-2’,6’-dimethoxybiphenyl, SPhos) through theFeCl3catalyzed Fridel–Crafts reaction. Triph–SPhos obtained with SPhoscopolymerized in could be further functionalized with PdCl2to formPdCl2@Triph–SPhos Such catalyst could be used in the Suzuki–miyaura couplingreactions of aryl halides (aryl chloride) with arylboronic acid and proceed in excellentyield. Meanwhile, such materials can be used as multi-functional catalyst in reactionssuch as Buchwald–Hartwig reactions and the formation of diphenyl ether.3. The microporous organic nanotube material, donated as MONT, wassynthesized through the palladium catalyzed Sonogashira reaction of1,3,5-triethynylbenzene and4,4’-dibromobiphenyl-2,2’-diamine. Several factors suchas the solvents used and monomers of diverse aryl halides were considered whichinfluenced the nanotube formed in the synthesis process. The MONT obtained herecan be used as one kind of host material to support the loading of noble metalnano-particles such as Au and Pd. With the addition of different reduction agent suchas hydrazine hydrate, sodium borohydride and borane, the conditions for thepreparation of noble metal nano-particles can be optimized.4. Great efforts have been paid here on the development of four-connectedmetal–organic frameworks here. First, we’ve present here for the first time a4+4strategy for the construction of a zeolitic metal–organic framework, donated as(Et2NH2)[In(BCBAIP)]·4DEF·4EtOH (BCBAIP: 5-(bis(4-carboxybenzyl)amino)isophthalic acid). Such a compound was constructedby tetrahedral four-connected ligand and four-connected {In(O2C)4} group with theSOD topology. This compound possesses anionic framework and nano-sized sodalitecage, which enables it to adsorb dyes, especially cationic dyes. Furthermore, thecoumarin6and coumarin343loaded compound1exhibit efficient light-harvestingproperties. Then, several semi-rigid ligands were employed here to construct a seriesof four-connected materials. Due to that these ligands can exhibit diverse geometrieswith the free rotation through characteristic bonds or functional groups, these ligandswith quadrangle or tetrahedron building blocks can be formed in the formation ofthese frameworks. These materials, donated [Mn2(TADIP)(DMF)3]·DMF (2),[Co2(TADIP)(DEF)3]·DEF (3),[Mn2(BCBAIP)(DMF)3]·7.5DMF (4) and(Me2NH2)[In(DBIP)]·3DMF·7H2O (5), were obtained. The topological analyses ofthese compounds reveal the formation of Pts, ABW, SOD and Unc topologies,respectively.5. Different metal–organic frameworks with luminescent properties wereprepared and used for the detection usages. First, two unsymmetrical ligands weredesigned and synthesized. The unsymmetrical1,2,3-triazole-containingtetracarboxylate ligand (H4TADIP) was synthesized through the copper-catalyzedazide–alkyne cycloaddition (CuAAC) reaction of diethyl-5-azidoisophthalate anddiethyl-5-ethynylisophthalate. The unsymmetrical alkynyl-containing tricarboxylateligand (H3CPEIP) was synthesized by the Sonogashira coupling reaction of5-ethynylisophthalic acid and ethyl4-iodobenzoate. H3CPEIP was used to react withthe non-oxo trinuclear cadmium for the preparation of a novel luminescent3-DCd-MOF [Cd3(CPEIP)2(DMF)3]·solvent (solvent=DMF·C2H5OH·2H2O)(6).Furthermore, the micrometer-sized compound Cd-MOF was also synthesized andused as a sensitive sensor for detection of aromatic explosives. H4TADIP was used tocoordinate with the lanthanide elements and a family of lanthanide MOFs, donated as[La(HTADIP)(H2O)4]·xH2O (2<x <2.5)(7),[Eu(HTADIP)(H2O)4]·H2O (8),[Tb(HTADIP)(H2O)3]·2H2O (9), and [Er(HTADIP)(H2O)3]·2H2O (10), was obtained here. These compounds are three-dimensional and isostructural frameworks withsmall differences in the coordinated terminal and lattice water molecules. Theluminescent properties of8and9were investigated and the magnetic properties of9and10were studied. Compound9exhibits good selective luminescent sensingbehavior to Cu2+ions in aqueous solution.