Alkali Cation Ligating Iodocuprate(I)-Based Coordination Networks with the Thiacrown Ether 1,10-Dithia-18-crown-6

We report two phases containing the hexagonal (6,3) network of the graphene sheet derived by tridentate coordination of 1,3,5-benzenetricarboxylate to octahedral NiII centers. When the solvent used is 2-methyl-1-butanol, water directs the coordination about NiII and BCAʹBʹCʹ stacking of layers is obtained. The use of 1-butanol as solvent gives a different hydrogen-bonding arrangement around NiII and produces AAA stacking of the layers. We have previously demonstrated that the use of other alcohols such as methanol, ethanol, 1,2ethanediol, and 1,2-propanediol leads to the formation of 3-D architectures. Here we show that a change in the hydrogen bonding around the metal center leads to 2-D structures which house substantial solvent-filled microcavities. The comparatively weak interactions between layers, and the relative importance of framework-solvent interactions, facilitates slippage of the hexagonal sheets and interconversion between stacking type with guest exchange.