Optical Control of Directional Exciton Migration in Porphyrin‐Based Metal−Organic Frameworks

Abstract Porphyrin‐based metal‐organic frameworks (MOFs) have received great attention for solar photochemistry applications. Manipulating the direction of energy (exciton) migration plays an essential role in boosting the light‐harvesting efficiency of porphyrin‐based MOFs. Here, based on the time‐dependent exciton‐exciton annihilation rate, an optical control of directional exciton migration is demonstrated in cobalt‐porphyrin surface‐supported MOF nanofilms (Co‐TCPP SURMOFs). Utilizing photocarrier densities or lattice temperature as the control knob, the dynamic form of exciton migration in Co‐TCPP SURMOFs can be switched between the nearest‐neighbor 1D interaction and the quasi‐isotropic 2D interaction, which is well explained using a diffusion model of exciton‐exciton scattering. This results provide an optical approach to regulating exciton migration in MOFs, which enhances understanding of the excitonic behavior in artificial light harvesters.