Ship-in-a-Bottle Preparation of Long Wavelength Molecular Antennae in Lanthanide Metal-Organic Frameworks for Biological Imaging.

While metal-organic frameworks (MOFs) have been identified as promising materials for sensitizing near-infrared emitting lanthanide ions (Ln3+) for biological imaging, long-wavelength excitation of such materials requires large, highly delocalized organic linkers or guest-chromophores. Incorporation of such species generally coincides with fewer Ln3+ emitters per unit volume. Herein, the excitation bands of ytterbium-based MOFs are extended to 800 nm via the postsynthetic coupling of acetylene units to form a high density of conjugated π-systems throughout MOF pores. The resulting long wavelength excitation/absorption bands are a synergistic property of the composite material as they are not observed in the individual organic components after disassociation of the MOFs, thus circumventing the need for large organic chromophores. We demonstrate that the long wavelength excitation and emission properties of these modified MOFs are maintained in the biological conditions of cell culture (aqueous environment, salts, heating), pointing toward their promising use for biological imaging applications.