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What is the effect of different metal ion geometries on the formation and properties of coordination polymers and metal-organic frameworks? Provide specific examples and discuss their potential applications in catalysis or gas storage.

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The effect of different metal ion geometries on the formation and properties of coordination polymers and metal-organic frameworks  MOFs  is significant, as it influences the overall structure, stability, and functionality of these materials. Coordination polymers and MOFs are formed by the self-assembly of metal ions or clusters with organic ligands, creating extended networks with various topologies and pore sizes. The geometry of the metal ions plays a crucial role in determining the connectivity and dimensionality of these networks.1. Linear geometry: Metal ions with a linear geometry, such as Ag I  and Au I , typically form one-dimensional coordination polymers. For example, Ag I  ions can coordinate with linear dicyanamide  N CN 2-  ligands to form a zigzag chain-like structure. These one-dimensional polymers can exhibit interesting properties such as luminescence and conductivity, which can be exploited in sensing and optoelectronic applications.2. Square planar geometry: Metal ions with a square planar geometry, such as Pt II  and Pd II , can form two-dimensional coordination polymers and MOFs. For instance, Pd II  ions can coordinate with tetrathiafulvalene  TTF  ligands to form a square grid-like structure. These materials can exhibit unique electronic properties, making them suitable for applications in molecular electronics and magnetic materials.3. Tetrahedral geometry: Metal ions with a tetrahedral geometry, such as Zn II  and Cd II , can form three-dimensional MOFs with high porosity. For example, Zn II  ions can coordinate with 1,4-benzenedicarboxylate  BDC  ligands to form the well-known MOF-5 structure. MOFs with tetrahedral metal ions often exhibit high surface areas and tunable pore sizes, making them ideal candidates for gas storage and separation applications.4. Octahedral geometry: Metal ions with an octahedral geometry, such as Fe III  and Cr III , can also form three-dimensional MOFs with diverse topologies. For example, Fe III  ions can coordinate with trimesic acid  H3BTC  ligands to form the MIL-100 structure, which exhibits a large pore size and high thermal stability. MOFs with octahedral metal ions can be used in catalysis, as their open metal sites can act as active centers for various chemical reactions.In summary, the geometry of metal ions significantly influences the formation, structure, and properties of coordination polymers and MOFs. By carefully selecting the metal ions and organic ligands, it is possible to design materials with specific topologies, pore sizes, and functionalities, which can be tailored for various applications in catalysis, gas storage, sensing, and electronics.

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