Improving Energy Transfer within Metal-Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis.

Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs. These linkers possess extended conjugation along one molecular axis, engendering low optical bandgaps and improved oscillator strength for their lowest-energy transition (S → S). This enhances absorption-emission spectral overlap and boosts the efficiency of Förster resonance energy transfer, which was observed experimentally by a sizable decrease in emission quantum yield (QY), accompanied by a faster population decay profile. We find that MOFs that orient these elongated linkers along their asymmetric pore channel, e.g., the hexagonal pores in an network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. The present study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.