Syntheses And Characterizations Of Inorganic Open-Framework Compounds Ternplated By Metal Complexes

Inorganic open-framework materials such as molecular sieves have beenextensively used in many industrial processes such as catalysis, adsorption andseparation, as well as in new applications of electronic, magnetism, chemical sensors,medicine, etc. Therefore, the preparation of new inorganic open-framework materialsis one of the most important fields for the material science. To synthesize newinorganic open-framework materials, the introduction of a structure-directing agent(SDA) is necessary. Conventional SDAs include alkali metal cations, alkaline earthcations, protonated organic amines, quaternary ammonium cations, metal complexescations and fluorine ions. Compared with conventional SDAs, metal complexescations can offer a particular spatial configuration, the wide range of oxidation states,more H-bonds, chiral symmetry and have an unexpected properties with the hostframework through the cooperative behavior, it is a focus at all times in thepreparation of inorganic materials.This thesis is focused on the synthesis of a series of open-framework compoundsunder the hydro/solvothermal conditions templated by metal complexes cations. Mainachievements are as follows:1. A novel three-dimensional gallogermanate zeolite [Ni(en)₃][Ga₂Ge₄O₁₂](GaGeO-CJ63) has been successfully synthesized under solvothermal condition.GaGeO-CJ63is a strictly4-connected zeolitic structure constructed exclusively bythree-ring building units, and its FD(framework density) is the third lowest among allknown zeolite frameworks. It contains10-ring channels along the three directions.GaGeO-CJ63was synthesized by using racemic [Ni(en)₃]²⁺ cations asstructure-directing agent, and chirality transfer could be clearly observed from chiraltemplates to chiral cages in its framework. GaGeO-CJ63is denoted as JST by theInternational Zeolite Association.2. A novel three-dimensional gallogermanate zeolite GaGeO-CJ64has beensuccessfully synthesized in the presence of chiral metal complexes in situ synthesismethod. Its inorganic structure is constructed by s6r(single6-ring), d6r(double6-ring), spiro-5building units. To the best of our knowledge, it is the first zeolite that contains11-ring intersecting channels along three directions. GaGeO-CJ64contains a novelvoid cage [3¹²Â·4³Â·6²Â·11⁶].3.[Co(en)₃]₂(Zr₂F₁₂)(ZrF₆H₂O)·H₂O and [Co(en)₃](Zr₂F₁₁H₂O), two compoundshave been successfully synthesized using different methods. Both compounds existextensive hydrogen bonds. Interestingly, they exhibit unusual photoelectronic effectsin the near-UV region. The fact that the signal of surface photovoltage of eachcompound is coincident with one of the UV/Vis absorption transitions of the cobaltamine complexes. This suggests that cooperative behavior between cobalt aminecomplexes and metal fluoride ions through interactions might be responsible for theseunexpected photoelectric phenomena.4. A new zinc phosphate structure [Co(NH₃)6]₃[Zn₈(HPO₄)₈(PO₄)₂](PO₄)(ZnPO-CJ68) with unusual double-sheet layers, has been successfully synthesized,which used cobalt hexaammine as the SDA. The structure of ZnPO-CJ68containsunusual layered host frameworks with interconnecting8-ring apertures along thethickness of the layers as well as in the planes of the layers. As the structural template,the guest cobalt hexaammine complex perfectly fits the shape of the intralayermicropore.5. A1D(one dimensional) infinite chain structure[Co(en)₃][Zn₂(H₂PO₄)(HPO₄)₂Cl₂] has been synthesized under hydrothermalcondition templated by [d,l-Co(en)₃]³⁺cations. It is constructed by a macro anionic[Zn₂(H₂PO₄)(HPO₄)₂Cl₂]_n^3-chain involving Zn-centered tetrahedra and P-centeredtetrahedral(ZnO₃Cl, H₂PO₄, HPO₄). It is rare that [Co(en)₃][Zn₂(H₂PO₄)(HPO₄)₂Cl₂]contains4-ring which consists of ZnO3Cl and HPO₄. Each4-ring is connected to forman infinite chain through PO₄tetrahedra. In addition, using cobalt amines cations astemplate, a2D layered Co(dien)2Al₃(PO₄)₄(AlPO-CJ54) has been prepared. Itsinorganic layer is constructed from strict alternation of AlO₄and PO₄tetrahetra toform zigzag ladder-type chains. The connectivity between the chains leads to anionic[Al₃P₄O₁₆]^3-layers. These layers only have four-and eight-membered rings. Thedisordered cobalt ammine complexes are located between layers.6. Two transition metal containing aluminophosphates MAPO-CHA(M=Zn,Mg)with CHA zeotype have been synthesized under the solvothermal conditions. Thelinkages of AlO₄(MO₄) tetrahedra and PO₄tetrahedra through vertex oxygen atoms form the inorganic framework [M₂Al₄(PO₄)₆]^2-. It contains8-ring channels along thethree directions. Nickel amine complexes are located in the cha cage to neutralize thenegative charge of the host.