Reabsorption‐Free Scintillating Hetero‐Ligand MOF Crystals Activated by Ultrafast Energy Transfer

Abstract Fast photoluminescence and scintillation with a Stokes shift larger than 1 eV is achieved in hetero‐ligand metal–organic framework (MOF) crystals comprising inorganic linking nodes and fluorescent conjugated ligands. By finely engineering the MOF composition with the use of ligands with strictly complementary emission and absorption properties and highly delocalized molecular electronic orbitals, the singlet excitons diffusion is enhanced through the ligand framework, fully exploiting both Förster and Dexter energy transfer mechanisms. This allows for the sensitization of energy acceptor ligand fluorescence by ultrafast non‐radiative energy transfer with a rate up to the THz range. This efficient antenna effect instantly activates the MOF scintillation with a Stokes shift as large as 1.3 eV in the blue spectral range, matching the highest sensitivity spectral window of the best photodetector available. This is obtained using a minimal doping level of the energy acceptor species, with a consequent elimination of emission re‐absorption that allows the achievement of a 500% increment of the MOFs scintillation efficiency and the detection of the radioactive krypton isotope ⁸⁵Kr from the gas phase with an improved sensitivity compared with the reference material.