Syntheses, Characterizations And Properties Of Phosphonates And Sulfonates Inorganic-organic Hybrid Materials

Inorganic-organic materials are recently of great interest due to their potential applications in adsorption, separation and catalysis. Since Robl and Clearfield have developed synthetic route using organic polyfunctional group molecule, such as phosphonic acid, carboxylic acid and sulfonic acid, as linker to form complexes with inorganic compounds, phosphonic acids, carboxylic acids and sulfonic acids with multi-sites ligands are more and more paid close attention. These materials may be employed in the field of semiconductor, ion exchange, catalysis, molecular magnets, proton conduction, nonlinear optical materials, inserted chemistry and photochemistry, thereby promoting rapid development of the phosphonate and sulfonate's materials.Phosphonate chemistry rise in the mid-1970s. With 30 years gonging by, metal phosphonates containing from +2 to +6 valence have been reported. In recent years, based on the addition of organic template and using of a variety of organic functional groups to perform a chemical modification, as well as hydrothermal synthesis, these methods not only have provide a broader space for the preparation of phosphonates, but also to study their applications has supply with a solid foundation. phosphonates containing multi-functional, zero-dimensional (clusters), one-dimensional, two-dimensional, three-dimensional structure and open framework of using organic amine as template, have been increasing in number. High-dimensional and low-dimensional(cluster) phosphonates are relative rare. Phosphonates with pore and zero-dimensional multinuclear magnetic metal are the research topic of the day, because the potential applications in the field of adsorption or ion exchange for hole phosphates and showing magnetic phenomena in an orderly manner for some zero-dimensional polynuclear phosphonates with some physical properties such as magnetic quantum tunnels—this kind of single-molecular magnets can be used as magnetic storage equipment materials. However, the phosphonic acid used in synthesis of these compounds are relatively limited, corresponding phosphonates reported being more scarce. Thus, by controlling the pH value of solution, we select three phosphonic acid, H₂O₃PCH₂N (CH₂CO₂H)2 (H₄L¹), (H₂O₃PCH₂)2NCH₂CO₂H (H₅L²), H₂O₃PCH₂N(C₂H₄) 2NCH₂PO₃H₂ (H₄L³) to synthesize seven phosphonates successfully.However, study on sulfonate ligands have been attracted attention only in recent years. Both organic sulfonic acid (R–SO₃^–) and phosphonic acid group (R–PO₃^2-) structure are very similar, but they possess different charge and the different ability of the formation of hybrid materials. The bonded ability between metal-oxygen in organic sulfonate is weaker than that of in phosphonate. If we can find the appropriate soft metal ions, in some cases sulfonic group compete with the water molecules to coordinate with metal ion, and stable structural compounds would be obtained. At present the synthesis of organic sulfonates containing a variety of functional groups is emerging as a hot area. Because introducing carboxyl and amino, nitrogen heterocyclic groups into organic sulfonates not only make structure rich and colorful but also result in the possible application. From the point of view of the synthesis, introduction of new functional groups both increases solubility of organic acid in the water, but also provides more coordinated sites and coordination modes. Accordingly, we introduce NaH₂SIP into the system of the synthesis. According to the literature, organic amine used in the synthesis are the most rigid or semi-rigid, and flexible organic amine in the synthetic system seldom reported. In this thesis, we described the synthesis, crystal structure and some properties of a series of metal (Ni, Co, Mn, Pb) phosphonates, matal (Mn, Pb) sulfonates and metal-organic(Cd, Ni) chlorids, and summarized the rules of synthesis and compared the difference of structures and synthesis.Under mild sovlothermal conditions, two phosphonates (NH₄)₂[Ni(L¹)(H₂O)] (1) with one-demensional chain and (H₃O)₈[Ni₄O₂(HL¹)₄(H₂O)₂] (2) with tetranuclear cluster structure have been synthesized and characterized by single crystal X-ray diffraction. The construction of 1D chain structure in the compound 1 can be viewed as the assembly of octahedral [NiO₅N] building units and carboxylate groups in cis-trans mode, being different from those of reported compounds in which the phosphonate group or 4,4'-bpy bridges metal to produce 1D chain. Magnetic analytic result indicates there is an antiferromagnetic coupling between Ni(II) ions in the chain. In the process of synthesizing compound 1, compound 2 is obtained at the same time. compound 2 possesses tetranuclear structure built from carboxylate groups in cis-trans mode. Magnetic analytic result indicates there is a spin-canting antiferromagnetic coupling between Ni(II) ions. compound 2 reveals the better fluorescence owing to the formation of multinuclear clusters. Under mild sovlothermal conditions, three phosphonates[NH₃(CH₂)₃NH₃](NH₄)₄[Ni(L²)(H₂O)]₂ (3), (H₃O)₃[Ni(L²)(H₂O)₂]·4H₂O (4) and (H₃O)[Co(H₂L²)(H₂O)₂]·2H₂O (5) have been synthesized and characterized by single crystal X-ray diffraction. By adjusting pH value of solution, compound 3 is obtained. Compound 3 is a 3D supramalecule constructed from binuclear building unit, at the same time organic amine is located at among tetraclusters. So organic amines can not only adjust pH value of solution but also perform the function of template and structure-directing agents. Magnetic analytic result indicates ferromagnetic coupling interactions is prominent between Ni(II) ions above 7 K. Using TMAOH instead of 1,3-PDA, compounds 4 and 5 are obtained. Their coordination mode with H5L2 ligand are similar, but belong to different space group attributed to metal ionic electronic configuration of the outer. With organic amine study, we found that the template size decreases, compounds tend to generate low-nuclear structure. Water chain is the first be found which lead to form 3D supramalecular network in the compound 4. The formation of water chain both increases structural stability and make compound possibly have property. Magnetic analytic result indicates ferromagnetic coupling interactions is prominent between Ni(II) ions above 40 K in compound 4, but antiferromagnetic coupling for compound 5. Both compounds 2 and 4 reveal the better fluorescence, however compound 5 doesn't show fluorescence owing to metal ionic electronic configuration of the outer.Herein, We discuss the syntheses and structural features of these novel compounds and the structural relationships among them. In addition, we find that F– ion is a very important effect factors for the synthesis of phosphonates.We successfully prepared two phosphonates under mild hydrothermal synthesis conditions, namely, [Mn(H₂L³)]·2(H₂O)_1/2 (6) and [Pb₂(HL³)]·(NO₃)·2(H₂O) (7). 3D framework structure with one-dimensional channels is formed through organic moiety PIP of ligand connecting with inorganic chain in compound 6. 2D layer structure is built up from organic moiety PIP linking with inorganic chain in compound 7. It is noteworth that compound 7 is new 2D layer example with positive charge [Pb₂(HL₃)]⁺.Two sulfonates are isolated from hydrothermal and water–ethanol system, respectively, namely [H₃N(CH₂)₃NH₃][Pb₂(SIP)₂]·6H₂O (8) and [Cd(HSIP)(PIP)(H₂O)₂] (9). The crystal structure of compound 8 is built up from dinuclear units [Pb₂O₂], through bridging sulfonate group giving rise to 2D layer structure. The octahedra {CdO₅N} as the basic building unit are connected by carboxylate group of ligand, producing 1D chain structure in the compound 9. Both 8 and 9 can form 3D supramolecular network by hydrogen-bond interactions. The compounds 8 and 9 both reveal the better fluorescence.Using different organic amine as template agents, one one-dimensional compound 10, namely {CdCl₃[(CH₃)₃NH]} (10), and two three-dimensional open-framework compounds 11, 12, namely [NiCl₂(C₄N₂H₈)] (11) and [CdCl₂(C₄N₂H₈)] (12), are prepared from sovlothermal and water-ethanol system, respectively. The connectivity between Cd(II) ions and chlorin ions gives rise to a inorganic anionic chain architecture [CdCl₃]^n– in the compound 10. Interactions of static electricity force between inorganic anionic chain [CdCl₃]^n– and trimethylamine cations gives rise to the formation of supramalecule. TGA-DTA analysis exhibits that framework of compound 10 starts collapse until the temperature rising up to 410°C, showing the higher thermal stability. In the solid state compound 10 exhibits intense photoluminescence (λmax = 631 nm) at excite band 464 nm. They may be good candidates for blue-light emitting diode devices, since these condensed materials are highly thermally stable and insoluble in common polar and non-polar solvents. The compounds 11 and 12 are isostructural, and possess 3D open-framework structure with one-dimensional channels constructed through connectivity PIP molecules with neutro-inorganic chain. Magnetic measure result reveals that ferromagnetic coupling interactions is prominent between Ni(II) ions above 55 K in compound 11. In the solid state compound 11 exhibits the stronger photoluminescence. The adsorption result shows that the compound 12 can adsorb the nitrogen with a Langmuir surface area of 153.7 m²/g and a pore volume of 0.1561 cm³/g, which can be attributed to the dynamic feature of the framework.In this paper, we reviewed the syntheses and structural characterization of a series of Ni^II, Co^II, Mn^II, Pb^II phosphonates, Mn^II, Pb^II sulfonates and inorganic-organic hybrid Cd^II and Ni^II chlorids. These results show that it is possible to prepare structural complex structural metal phosphonates, sulfonates and chlorids based on demands by transferring different organic amines and adjusting proper reagents molar compostions.