Implementing chemical functionality into oriented films of metal–organic frameworks on self-assembled monolayers

The generation of thin films of oriented functionalized metal–organic frameworks (MOFs) on self-assembled monolayers was achieved via direct growth from solution. Specifically, the direct growth from solvothermally pretreated synthesis solutions of two different MOF structures with amino functionality was investigated: the flexible framework structure NH2–Fe–MIL-88B and the mesoporous MOF NH2–Fe–MIL-101 with its remarkably large unit cell. Both MOF structures can be grown in a highly oriented fashion on self-assembled monolayers of 16-mercaptohexadecanoic acid on gold. With the help of a quartz crystal microbalance we demonstrate that the introduction of amino groups into the framework strongly affects the host–guest interactions towards ethanol molecules: thin films of NH2–Fe–MIL-88B show a significantly higher uptake of ethanol than unfunctionalized Fe–MIL-88B films. In situXRD experiments during sorption of ethanol showed that the amino group does have an impact on the cell parameters of the structure, but the flexibility (“breathing”) during ad- and desorption of ethanol is similar for the functionalized and the unfunctionalized structures. It is anticipated that the implementation of chemical functionalities into oriented MOF films will lead to selective host–guest interactions that are of key importance for chemical sensing and other applications.