Control of Interpenetration in Two-Dimensional Metal–Organic Frameworks by Modification of Hydrogen Bonding Capability of the Organic Bridging Subunits

Six coordination polymers were prepared by linking Mn(SCN)2 units by three different bis(4-pyridyl) substituited hydrazone derivatives (L) in three different solvents (methanol, ethanol, and acetonitrile) in order to study the effect of the hydrogen bonding ability of L on the formation of solvates rather than interpenetrated solvent-free interpenetrated structures. When the ligand L which cannot act as a hydrogen donor was used, in all three solvents the same product was obtained. This was a [Mn(SCN)2 L 2] n metal–organic framework, consisting of two-dimensional (2D) networks, each interpenetrating two neighboring ones. When the bridging ligands L have additional functional groups capable of acting as hydrogen donors or acceptors, synthesis from acetonitrile yields non-interpenetrating 2D [Mn(SCN)2 L 2] n networks with solvent molecules occupying the voids of the network. Other solvents were found to yield interpenetrated solvent free networks, or they replaced some of the L ligands, forming one-dimensional coordination polymers.