Rozprawy doktorskie na temat „Organic-Inorganic Hybrid Nanoporous Phosphates”

博士
國立清華大學
化學系
99
In this research, 18 compounds were synthesized by employing organic amine as template under hydrothermal conditions. They were classified into three systems: System A put emphasis on reduction of energy consumption and chemical recycling of waste PET. Reactions with the use of microwave as an energy source largely cut down the reaction time to 1% as compared to conventional heating time and successfully yielded three single-phased products of A1, A2 and A3. The compounds A2,A3 and A5 displayed 3D structures “seemingly the same “ but they are not exactly identical due to the common organic linkers of BDC moiety adopting different orientations with respect to the same inorganic framework. The results should overturn our conventional cognition on scaling up product by microwave synthesis. On the other hand, scraps of waste PET bottle were successfully employed in two reactions as potent reagents to produce new compound A5 and high-valued phosphor materials A6 with potential application to white-light LEDs, providing a brand new perspective to chemical recovery of waste PET. System B contains six layered zinc phosphates encapsulating organic supra molecules as guest species. Bearing intricate hydrogen-bonding patterns within each layer, the pseudo-neutral (H3tren)2[Zn3(PO4)4] sheets are highly adaptable to varied achiral organic monomers, making them transformed into different chiral supramolecular chains. As a result, the entire structures of B1-B4 were turned into chiral as well. Depending on the molecular size of guest monomers, the layer gap was able to pop up the most to 2.01 nm (B4). Furthermore, the zinc center could be doped with homo-valence transition metal ions. Incorporation of Co2+ ions into layers exerted strong influence on supramolecular guests’ arrangements while doping of Mn2+ ions created novel photoluminescence property-the inter-layer supramolecular guest became a good sensitizer for the emission of bright orange- (from B1-Mn) or pink- (from B4-Mn) light under UV excitation. System C involved the use of bola-type surfactant, the long chain amine-DADD, as organic template. In the synthesis additional bulky organic acid-BPDA was included together with (metal) phosphate to generate six layered materials. The compound of C3 is highly interesting as it not only was observed ultra-large inter layer gap of 2.2nm but also revealed intriguing green afterglow property. In the three systems, every structure was well-characterized and extended to the discussion on their syntheses, thermal properties, self-assembly of supramolecular guests and the mechanisms of luminescence. The study generated significant results with substantial novelty and made conceptual breakthroughs to the field of organic/inorganic hybrid metal phosphate materials.

碩士
國立中央大學
化學學系
104
Two series of metal phosphate and phosphites structural, A and B, were shown as follows：(DA1)Zn2(Lcis)(HPO4)2 (A1)、(DA1)Zn2(Ltrans)(HPO4)2 (A2)、Zn3(L)0.5(DA2)(HDA2)(HPO3)2 (B1) and Co3(L)0.5(DA2)(HDA2)(HPO3)2 (B2). A1 and A2 were synthesized with the same reactants under the mild hydrothermal conditions. B1 and B2 had a similar structure with different metal center (B1 for Zn and B2 for Co). All of these structures were determined by single-crystal X-ray diffraction. Purity determined by PXRD, EA, XRF and EDX. 　　A1 and A2 are similar structure. BDC(L) bonded to Zn center with two different phases (cis and trans coordinate with metal). This is the first time we find in OMPO (organic-metallophosphate). By soaking A1 and A2 in Na+ solution, we found that DA1 were partially replaced by Na+ ion and ethanol. By the results of Element Analysis、Thermogravimetry Analysis and FTIR, we determined the new structure ：(DA1)0.5Na(C2H5OH)0.5Zn2(L)(HPO4)2. A1 and A2 had no luminescence properties. However, by soaking Eu3+ and Tb3+ ions solution, A1-Eu/Tb and A2-Eu/Tb had luminescence properties (green light for A1/A2-Tb and red light for A1/A2-Eu). 　　Soaking in Cu(NO3)2, powder color of B1 would turn white to blue by exchanging Cu ion for only an hour. B1 was also a good sensor for Cu2+ ion. The metal center of B2 was Co, which showed good magnetism. Determined by SQUID, B2 has paramagnetism in high temperature and antiferromagnetism in low temperature.

碩士
中原大學
化學研究所
97
Nine new coordination polymers, [Mg2(BTEC)(H2O)4]·2H2O (1)、 Mg2(BTEC)(H2O)6] (2) 、[Mg2(BTEC)(H2O)8] (3) 、 (H2tmdp)[Zn2(HPO4)2(BDC)] (4) 、 (H2tmdp)[CoxZn2-x(HPO4)2(BDC)] (x~0.6) (5) 、(H2tmdpp)[Zn2(HPO4)2(BDC)] (6) 、 (H2tmdpp)[CoyZn2-y(HPO4)2(BDC)] (y~0.8) (7) (BTEC = 1,2,4,5-Benzenetetracarboxylic acid；BDC = 1,4-benzene dicarboxylate anion；tmdp = 4,4’-trimethylene dipyridine ; tmdpp = 4,4'-Trimethylene dipiperidine have been synthesized by microwave reactions. The crystalline solids of 1 to 3 were prepared from the microwave reactions of magnesium (II) nitrate with H4BTEC under optimized ratios and different pH value controlled at different basic conditions. The results of crystal structure analysis displayed that these products have multi-dimensional structures, that is, 3D for 1, 2D for 2, and 1D for 3. A series of new organo-metallophosphate hybrid frameworks compound 4 to 7 with carboxylate-linked frameworks have been successfully synthesised by microwave-assisted reactions. All compounds were successfully synthesized by only 40 minutes at 160 oC using a microwave oven, compared to three days by conventional Solvothermal reactions. The resultant phases of compounds 4、5 were found to transform to porous phases by heating at 250 oC under vacuum. For the first time, as we known, the organo-metallophosphate hybrid frameworks of compound 4 and 5 were found to transform to foamy phases by heating at 300 oC in air. In summary, the single crystal structure analysis, thermal studies, photoluminescence, and gas adsorption of compounds 1-7 have been fully characterized.

Open-framework inorganic and inorganic-organic hybrid materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. Besides aluminosilicate zeolites, the metal phosphates and carboxylates constitute large families of open-framework structures. The possibility of building open architectures with the sulfate and selenate anions as the basic building units has been explored in this thesis. Investigations of a variety of open-framework metal sulfates and selenates, as well as a family of jarosites of different transition metals are presented. More importantly, studies directed towards the synthesis and understanding of the magnetic properties of various Kagome compounds formed by the transition metal ions is discussed at length. After providing an introduction to inorganic open-framework compounds (Part 1), the thesis presents the results of the investigations of various transition and rare earth metal sulfates with diverse structures and dimensionalities in Part 2. Some of these compounds show interesting properties. For example, a two-dimensional Ni(II) sulfate exhibits ferrimagnetism whereas a three-dimensional Ni(II) sulfate with 10-membered channels is paramagnetic. A family of three-dimensional co-ordination polymers of Co(II) sulfate wherein the Co(II) sulfate layers are linked by diaminoalkanes of varying chain length has been synthesized and characterized. Organically-templated neodymium and thorium sulfates with layered and three-dimensional structure have also been prepared. The jarosite family of compounds with the Kagome structure is considered as an ideal model for studying frustrated magnetism. This type of materials, however, is difficult to prepare in a pure and highly crystalline form. We have synthesized analogues of the jarosite containing magnetic ions other than Fe3+ by solvothermal techniques and discussed them in Part 3. In particular, we have prepared and explored the magnetic properties of Mn2+(S = 5/2), Fe2+ (S = 2), Co2+(S = 3/2) and Ni2+ (S = 1) jarosites. Based on the results presented, it becomes clear that the magnetic properties vary with the spin of the transition metal ion. It appears that those Kagome compounds with transition metalions with non-integer spins show antiferromagnetic interactions and magnetic frustration while those with integer spins exhibit ferro/ferrimagnetic properties. A theoretical study has also supports this observation. We have been able to isolate for the first time 1,4-diazacubane as the part of the structure of the nickel Kagome compound. The possibility of building open architectures with the selenate anion as the basic building unit has been explored in Part 4. The results have been rewarding and an organically-templated three-dimensional lanthanum selenate with 12-membered channels has thus been obtained for the first time.

Open-framework inorganic and inorganic-organic hybrid materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. Besides aluminosilicate zeolites, the metal phosphates and carboxylates constitute large families of open-framework structures. The possibility of building open architectures with the sulfate and selenate anions as the basic building units has been explored in this thesis. Investigations of a variety of open-framework metal sulfates and selenates, as well as a family of jarosites of different transition metals are presented. More importantly, studies directed towards the synthesis and understanding of the magnetic properties of various Kagome compounds formed by the transition metal ions is discussed at length. After providing an introduction to inorganic open-framework compounds (Part 1), the thesis presents the results of the investigations of various transition and rare earth metal sulfates with diverse structures and dimensionalities in Part 2. Some of these compounds show interesting properties. For example, a two-dimensional Ni(II) sulfate exhibits ferrimagnetism whereas a three-dimensional Ni(II) sulfate with 10-membered channels is paramagnetic. A family of three-dimensional co-ordination polymers of Co(II) sulfate wherein the Co(II) sulfate layers are linked by diaminoalkanes of varying chain length has been synthesized and characterized. Organically-templated neodymium and thorium sulfates with layered and three-dimensional structure have also been prepared. The jarosite family of compounds with the Kagome structure is considered as an ideal model for studying frustrated magnetism. This type of materials, however, is difficult to prepare in a pure and highly crystalline form. We have synthesized analogues of the jarosite containing magnetic ions other than Fe3+ by solvothermal techniques and discussed them in Part 3. In particular, we have prepared and explored the magnetic properties of Mn2+(S = 5/2), Fe2+ (S = 2), Co2+(S = 3/2) and Ni2+ (S = 1) jarosites. Based on the results presented, it becomes clear that the magnetic properties vary with the spin of the transition metal ion. It appears that those Kagome compounds with transition metalions with non-integer spins show antiferromagnetic interactions and magnetic frustration while those with integer spins exhibit ferro/ferrimagnetic properties. A theoretical study has also supports this observation. We have been able to isolate for the first time 1,4-diazacubane as the part of the structure of the nickel Kagome compound. The possibility of building open architectures with the selenate anion as the basic building unit has been explored in Part 4. The results have been rewarding and an organically-templated three-dimensional lanthanum selenate with 12-membered channels has thus been obtained for the first time.

Open–framework inorganic materials are an important class of compounds because of their many applications in the areas of ion–exchange, separation and catalysis. Ever since the discovery of microporous aluminophosphates by Flanigen and co–workers in the early 80’s, the field of open–framework compounds has witnessed explosive growth. It is now established that the open–framework compounds comprise of almost all the elements of the periodic table. In addition, it has been shown that the inorganic anions in the open–framework compounds can be partially substituted by rigid organic linkers such as the oxalate. The resulting inorganic–organic hybrid structures are interesting due to the variable nature of the binding properties of the organic and inorganic moieties. The present thesis consists of systematic studies on the formation of amine–templated inorganic open–framework structures and inorganic–organic hybrid compounds based on the main group, transition metal and actinide elements. In Chapter 1 of the thesis an overview of inorganic open-framework materials is presented, with an emphasis on the elements that have been employed in the present study. Chapter 2 has two parts (Parts A and B) describing the synthesis and structure of open-framework tin(II) containing compounds. In Part A, the syntheses and structures of amine–templated tin(II) phosphates are presented, and in Part B, the syntheses and structures of a family of tin(II) oxalate compounds are discussed. Weak intermolecular forces such as hydrogen-bond interactions, π•••π interactions, and lone-pair–π interactions have been observed in these compounds, and appear to lend structural stability. As part of this study, efforts have been made to evaluate the energies associated with the π•••π interactions and the lone-pair–π interactions using suitable theoretical models. In Chapter 3, a new family of organically templated hybrid materials based on indium, synthesized by partially substituting the inorganic anion (phosphite/phosphate/suphate) by the oxalate group, is presented. These compounds exhibit a wide range of structures in which the oxalates play a variety of roles. The observation of the first zero-dimensional molecular hybrid structure and the isolation of concomitant polymorphic compounds is noteworthy. The molecular hybrid structure is reactive and undergoes transformation reactions under both acidic and basic conditions. In Chapter 4, the synthesis and structural studies of five new open–framework phosphate and phosphite compounds of gallium are presented. All the compounds have three-dimensional structures, and the formation of a gallium phosphate based on only one type of building unit (spiro–5) is noteworthy. While a large number of organically templated transition metal phosphates have been synthesized, studies on transition metal phosphites are not many. In Chapter 5, the synthesis, structure and magnetic properties of a family of transition metal (cobalt, vanadium, manganese) phosphite structures templated by the organic amines are presented. A previously known vanadyl phosphite has also been isolated and investigated by temperature dependent ESR and magnetic susceptibility studies. All the transition metal compounds exhibit antiferromagnetic behavior. In Chapter 6, the synthesis, structure, and transformation reactions in amine-templated actinide phosphonoacetates are presented. The compounds, which are based on uranium and thorium, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units, forming two– and three–dimensional structures. It has been shown that the two–dimensional uranyl phosphonoacetate–oxalate compound can be prepared by two different synthetic approaches: (i) solvent–free solid state reaction at 150˚C and (ii) room temperature mechanochemical (grinding) route. The formation of oxalate hybrids using the phosphonocarboxylate ligand is a new approach in the synthesis of multi-component hybrid compounds.

Open–framework inorganic materials are an important class of compounds because of their many applications in the areas of ion–exchange, separation and catalysis. Ever since the discovery of microporous aluminophosphates by Flanigen and co–workers in the early 80’s, the field of open–framework compounds has witnessed explosive growth. It is now established that the open–framework compounds comprise of almost all the elements of the periodic table. In addition, it has been shown that the inorganic anions in the open–framework compounds can be partially substituted by rigid organic linkers such as the oxalate. The resulting inorganic–organic hybrid structures are interesting due to the variable nature of the binding properties of the organic and inorganic moieties. The present thesis consists of systematic studies on the formation of amine–templated inorganic open–framework structures and inorganic–organic hybrid compounds based on the main group, transition metal and actinide elements. In Chapter 1 of the thesis an overview of inorganic open-framework materials is presented, with an emphasis on the elements that have been employed in the present study. Chapter 2 has two parts (Parts A and B) describing the synthesis and structure of open-framework tin(II) containing compounds. In Part A, the syntheses and structures of amine–templated tin(II) phosphates are presented, and in Part B, the syntheses and structures of a family of tin(II) oxalate compounds are discussed. Weak intermolecular forces such as hydrogen-bond interactions, π•••π interactions, and lone-pair–π interactions have been observed in these compounds, and appear to lend structural stability. As part of this study, efforts have been made to evaluate the energies associated with the π•••π interactions and the lone-pair–π interactions using suitable theoretical models. In Chapter 3, a new family of organically templated hybrid materials based on indium, synthesized by partially substituting the inorganic anion (phosphite/phosphate/suphate) by the oxalate group, is presented. These compounds exhibit a wide range of structures in which the oxalates play a variety of roles. The observation of the first zero-dimensional molecular hybrid structure and the isolation of concomitant polymorphic compounds is noteworthy. The molecular hybrid structure is reactive and undergoes transformation reactions under both acidic and basic conditions. In Chapter 4, the synthesis and structural studies of five new open–framework phosphate and phosphite compounds of gallium are presented. All the compounds have three-dimensional structures, and the formation of a gallium phosphate based on only one type of building unit (spiro–5) is noteworthy. While a large number of organically templated transition metal phosphates have been synthesized, studies on transition metal phosphites are not many. In Chapter 5, the synthesis, structure and magnetic properties of a family of transition metal (cobalt, vanadium, manganese) phosphite structures templated by the organic amines are presented. A previously known vanadyl phosphite has also been isolated and investigated by temperature dependent ESR and magnetic susceptibility studies. All the transition metal compounds exhibit antiferromagnetic behavior. In Chapter 6, the synthesis, structure, and transformation reactions in amine-templated actinide phosphonoacetates are presented. The compounds, which are based on uranium and thorium, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units, forming two– and three–dimensional structures. It has been shown that the two–dimensional uranyl phosphonoacetate–oxalate compound can be prepared by two different synthetic approaches: (i) solvent–free solid state reaction at 150˚C and (ii) room temperature mechanochemical (grinding) route. The formation of oxalate hybrids using the phosphonocarboxylate ligand is a new approach in the synthesis of multi-component hybrid compounds.