Functionalized and mixed metal -organic frameworks.
Steffek, Cory D.
2002
Abstract
Novel extended transition metal-organic frameworks have been prepared. The synthesis, characterization, and crystal structures of each compound is described. The reaction of cobalt sulfate pentahydrate with benzene triearboxylic acid demonstrates an alternative method for making MOF-0, a layered two-dimensional extended network. In addition to cobalt, analogous compounds are shown with nickel, magnesium, iron, manganese, and cadmium. Mixing of nickel and cobalt in different ratios shows that mixed metal frameworks can be tailored with controlled metal ion stoichiometry. Functionalization of the organic ligand using amino, hydroxy, and halogen functionality has been demonstrated. The reaction of 2-aminoterephthalic acid and zinc nitrate hexahydrate at room temperature yielded orange crystals of Zn(C<sub>6</sub>H<sub>5</sub>O<sub>4</sub>N)(DMF)<sub>1</sub>(ClC<sub>6</sub>H<sub> 5</sub>)<sub>0.25</sub> having the space group C2/m. The reaction of 2,5-dihydroxyterephthalic acid and copper nitrate hemihexahydrate at room temperature yielded Cu(C<sub> 6</sub>H<sub>4</sub>O<sub>6</sub>)(DMF)<sub>2</sub> crystallizing in the space group P2(1)/c, while the reaction of the same ligand with magnesium sulfate yielded Mg(O<sub>2</sub>C<sub>6</sub>O<sub>2</sub>H<sub>4</sub>O<sub>2</sub>)(DMF)<sub> 2</sub> in the space group C2/c. A halogenated aromatic, 2,3,5,6 tetrafluoroterephthalic acid, and copper nitrate hemihexahydrate yielded crystals of Cu<sub>4</sub>O<sub> 3</sub>(O<sub>2</sub>C<sub>6</sub>F<sub>4</sub>O<sub>2</sub>)(DMF)<sub>5</sub>(ClC<sub> 6</sub>H<sub>5</sub>)<sub>1</sub>(C<sub>3</sub>H<sub>5</sub>OH)<sub>1</sub>(H<sub> 2</sub>O)<sub>5</sub> in the space group P2<sub>1</sub>/n. The synthesis of three-dimensional porous metal formates has been demonstrated by reacting magnesium nitrate hexahydrate with two equivalents of formic acid. The analogous compound with iron has been demonstrated using iron (II) chloride hexahydrate with two equivalents of formic acid. Both crystallize in the space group P2<sub>1</sub>/n. The synthesis and properties of three isostructural three-dimensional terbium frameworks Tb(O<sub>2</sub>C<sub>16</sub>H<sub>8</sub>O<sub>2</sub>)<sub> 1.5</sub>(DMF)<sub>3</sub>, Tb(O<sub>2</sub>B<sub>10</sub>H<sub>10</sub>O<sub> 2</sub>)<sub>1.5</sub>(DMF)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>, Tb(O<sub> 2</sub>C<sub>6</sub>O<sub>2</sub>H<sub>4</sub>O<sub>2</sub>)<sub>1.5</sub>(DMF)<sub> 3</sub>, are presented. Each network reveals a dinuclear [Tb(L)<sub>1.5</sub>(DMF)<sub> 1</sub>]<sub>2</sub> (L = O<sub>2</sub>C<sub>16</sub>H<sub>8</sub>O<sub>2 </sub>, O<sub>2</sub>B<sub>10</sub>H<sub>10</sub>O<sub>2</sub>, O<sub>2</sub>C<sub> 6</sub>O<sub>2</sub>H<sub>4</sub>O<sub>2</sub>) complex which incorporates two bridging carboxylates, and one non-bridging carboxylate. All three compounds crystallize in the space group P(-1). The reaction of pentaerythritol with titanium isopropoxide in a solution of pyridine at room temperature yielded colorless plates, which was formulated as Ti<sub>8</sub>[C(CH<sub>2</sub>O)<sub>4</sub>]<sub>4</sub>[OCH(CH<sub> 3</sub>)<sub>2</sub>]<sub>16</sub>. The single crystal structure analysis revealed a dimer in the unit cell of the triclinic space group P1¯.Subjects
Frameworks Functionalized Isostructure Metal-organic Microporous Mixed-metal
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