Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping

Metal–organic frameworks (MOFs) with light-harvesting building blocks designed to mimic photosynthetic chromophore arrays in green plants provide an excellent platform to study exciton transport in networks with well-defined structures. A step-by-step exciton random hopping model made of the elementary steps of energy transfer between only the nearest neighbors is usually used to describe the transport dynamics. Although such a nearest neighbor approximation is valid in describing the energy transfer of triplet states via the Dexter mechanism, we found it inadequate in evaluating singlet exciton migration that occurs through the Forster mechanism, which involves one-step jumping over longer distance. We measured migration rates of singlet excitons on two MOFs constructed from truxene-derived ligands and zinc nodes, by monitoring energy transfer from the MOF skeleton to a coumarin probe in the MOF cavity. The diffusivities of the excitons on the frameworks were determined to be 1.8 × 10–2 cm2/s and 2.3 × 1...