Imparting Functionality to MOF Nanoparticles by External Surface Selective Covalent Attachment of Polymers

Selective functionalization of the external surface of porous nanoparticles is of great interest for numerous potential applications in the field of nanotechnology. Regarding metal–organic frameworks (MOFs), few methods for such modifications have been reported in the literature. Herein, we focus on the covalent attachment of functional polymers on the external surface of MIL-100­(Fe) nanoparticles in order to implement properties such as increased chemical and colloidal stability or dye-labeling for the investigation of the particles by fluorescence based techniques. We prove covalent nanoparticles-polymer bond formation by liquid NMR after dissolution of the functionalized MOF under mild conditions and estimate the amount of covalently attached polymer by UV–vis spectroscopy. The functionalization of the MOF nanoparticles with fluorescently labeled polymers enables the investigation of nanoparticle uptake into tumor cells by fluorescence microscopy. Furthermore, the influence of the polymer shell on the magnetic resonance imaging activity of MIL-100­(Fe) is investigated in detail. The functionalization approach presented here is expected to enable the fabrication of hybrid nanomaterials, extending the enormous chemical space of MOFs into polymer materials