Variations on a One-Dimensional Theme:  The Hydrothermal Syntheses of Inorganic/Organic Composite Solids of the Iron Molybdate Family

Abstract

The hydrothermal reactions of molybdenum oxide starting materials with iron(II) and iron(III) halides in the presence of 2,2‘-bipyridine have afforded the three related one-dimensional solid materials [MoO 4 {Fe(III)Cl(2,2‘-bpy)}] ( 1 ), [Mo 3 O 12 {Fe(III)(2,2‘-bpy)} 2 ]·0.25H 2 O ( 2 ), and [Mo 4 O 15 {Fe(III)(2,2‘-bpy)} 2 ] ( 3 ). The structures of these three materials are based on a common one-dimensional ribbon exhibited by 1 . The ribbon is constructed from four-polyhedra rings consisting of two {MoO 4 } tetrahedra and two {FeXN 2 O 3 } (X = Cl for 1, O for 2 and 3 ) octahedra. These polyhedra corner share such that each molybdenum center serves to bridge the two iron octahedra in the ring. Attachment to the next such four-ring is through the third corner sharing interaction of each molybdenum tetrahedron. Replacement of the pendant chloride substituents on adjacent iron centers in 1 with an {MoO 4 } unit leads to compound 2, while an {Mo 2 O 7 } linkage between adjacent iron centers affords 3 .