Synthesis And Characterization Of Inorganic Framework Transition Metal Sulfate And Zeolitic Coordination Polymers

Inorganic porous materials have served for extensive applications in catalysis, ion-exchange, separation, absorption, host-guest chemistry°wing to their regular pore architectures and excellent surface area. Therefore, design and synthesis°f new inorganic porous materials, such as the zeolite-like phosphates, arsenates, selenates, selenites, germinates, phosphites, which involve tetrahedral [TO₄] units (T=tetrahedrally coordinated atoms) have attracted much attentions°f scientists. Similarly, metal sulfates also contain [TO₄] units that are known to promote a wide range°f structural arrangement in inorganic solids. However, they have been°bserved hardly to generate the architectures with°pen-frameworks while condensed°r low-dimensional architectures are currently predominant°ver the metal sulfate compounds due to the hydrothermal synthesis. In this dissertation, we report solvothermal synthesis°f the metal sulfates in the water-poor solvent (CH₃COOH,DMA) that has afforded five novel transition metal sulfates: (NH₄)₈[Co₈(SO₄)₁₂] (1):°rthorhombic, space group P2₁,a=10.0023(12) A, b=10.002 A, c=10.002 A,α=β=γ=90.00°, exhibiting a three-dimensional structure; Co₁₂(SO₄)₁₂ (2): monoclinic, space group C₂/c, a = 12.644(4) A, b = 12.702(4) A, c = 6.480(2) A,α= 90.00°,β= 115.163(5)°,γ= 90.00°, displaying zeolite-like topology structure; (NH₄)₂[Zn(SO₄)₂] (3):°rthorhombic, space group P2₁2₁2₁, a = 6.8592(9) A, b = 8.9750(11) A, c = 13.7210(17) A,α=β=γ= 90.00°, revealing a chiral diamondoid framework; Zn₂(SO₄)₂(C₁₀H₈N₂) (4):°rthorhombic, space group Pccn, a = 9.5841(16) A, b = 22.054(4) A, c = 6.8224(12) A,α=β=γ= 90.00°, exhibiting a three-dimensional structure; (C₄N₂H₁₂)₂Mn₂(SO₄)₂Cl₄ (5): monoclinic, space group P2₁/c, a = 11.8375(17) A, b = 14.874(2) A, c = 12.1665(17) A,α= 90.00°,β= 104.637(2)°,γ= 90.00°, displaying a°ne-dimensional chain.In this dissertation we also choose 2-butyl imidazole (buim) as the role°f O^2- and Cd²⁺, Zn²⁺ as the T atom°f the zeolites. We have successfully synthesized two°f coordination polymers°f [Cd(buim)₂] (6), [Zn(buim)₂] (7) with the zeolitic ANA topology.