Cherenkov Radiation-Mediated In Situ Excitation of Discrete Luminescent Lanthanide Complexes

Lanthanide luminescence, while ideal for in vivo applications owing to sharp emission bands within the optical window, requires high-intensity, short-wavelength excitation of small organic "antenna" chromophores in the vicinity of the lanthanide complex to access excited f-orbital states through intersystem crossing. Herein, we explored Cherenkov radiation of the radioisotopes ¹⁸ F and ⁸⁹ Zr as an in situ source of antenna excitation. The effective inter- and intramolecular excitation of the terbium(III) complexes of a macrocylic polyaminocarboxylate ligand (hydration number (q)=0, quantum yield (φ)=47 %) as well as its analogue functionalized to append an intramolecular Cherenkov excitation source (q=0.07, φ=63 %) was achieved. Using conventional small-animal fluorescence imaging equipment, we have determined a detection limit of 2.5 nmol of Tb(III) complex in presence of 10 μCi of ¹⁸ F or ⁸⁹ Zr. Our system is the first demonstration of the optical imaging of discrete luminescent lanthanide complexes without external short-wave excitation.