Solid State and Solution Mediated Multistep Sequential Transformations in Metal–Organic Coordination Networks

Sequential transformation in a family of metal–organic framework compounds has been investigated employing both a solid-state as well as a solution mediated route. The compounds, cobalt oxy-bis(benzoate) and manganese oxy-bis(benzoate) having a two-dimensional structure, were reacted with bipyridine forming cobalt oxy-bis(benzoate)-4,4′-bipyridine and manganese oxy-bis(benzoate)-4,4′-bipyridine, respectively. The bipyridine containing compounds appear to form sequentially through stable intermediates. For the cobalt system, the transformation from a two-dimensional compound, [Co(H2O)2(OBA)] (OBA = 4,4′-oxy-bis(benzoate)), I, to two different three-dimensional compounds, [Co(bpy)(OBA)]·bpy, II, (bpy = 4,4′-bipyridine) and [Co(bpy)0.5(OBA)], III, and reversibility between II and III have been investigated. In the manganese system, transformation from a two-dimensional compound, [Mn(H2O)2(OBA)], Ia, to two different three-dimensional compounds, [Mn (bpy)(OBA)]·bpy, IIa and IIa to [Mn(bpy)0.5(OBA)], IIIa, has been investigated. It has also been possible to identify intermediate products during these transformation reactions. The possible pathways for the formation of the compounds were postulated.