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 (<b>L</b>) in three different solvents (methanol, ethanol, and acetonitrile) in order to study the effect of the hydrogen bonding ability of <b>L</b> on the formation of solvates rather than interpenetrated solvent-free interpenetrated structures. When the ligand <b>L</b> which cannot act as a hydrogen donor was used, in all three solvents the same product was obtained. This was a [Mn­(SCN)₂<b>L</b>₂]_<i>n</i> metal–organic framework, consisting of two-dimensional (2D) networks, each interpenetrating two neighboring ones. When the bridging ligands <b>L</b> have additional functional groups capable of acting as hydrogen donors or acceptors, synthesis from acetonitrile yields non-interpenetrating 2D [Mn­(SCN)₂<b>L</b>₂]_<i>n</i> 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 <b>L</b> ligands, forming one-dimensional coordination polymers