Chemistry of SURMOFs: Layer-Selective Installation of Functional Groups and Post-synthetic Covalent Modification Probed by Fluorescence Microscopy

Layer-selective installation of functional groups at SURMOFs (surface-attached metal−organic framework multilayers) is reported. Multilayers of [Cu(ndc)(dabco)0.5] grown in [001] orientation on pyridine-terminated organic self-assembled monolayers on Au substrates were functionalized with amino groups by step-by-step liquid-phase epitaxy. The method allows the growth of samples exhibiting one monolayer of functional groups at the external thin-film surface. In situ quartz crystal microbalance monitoring confirmed the presence of amino groups by turning the multilayer film from a non-reactive to a reactive material for covalent binding of fluoresceinisothiocyanate, and fluorescence microscopy displays the expected luminous property.