Dipole-mediated exciton management strategy enabled by reticular chemistry.

Selectively blocking undesirable exciton transfer pathways is crucial for utilizing exciton conversion processes that involve participation of multiple chromophores. This is particularly challenging for solid-state systems, where the chromophores are fixed in close proximity. For instance, the low efficiency of solid-state triplet-triplet upconversion calls for inhibiting the parasitic singlet back-transfer without blocking the flow of triplet excitons. Here, we present a reticular chemistry strategy that inhibits the resonance energy transfer of singlet excitons. Within a pillared layer metal-organic framework (MOF), pyrene-based singlet donors are situated perpendicular to porphyrin-based acceptors. High resolution transmission electron microscopy and electron diffraction enable direct visualization of the structural relationship between donor and acceptor (D-A) chromophores within the MOF. Time-resolved photoluminescence measurements reveal that the structural and symmetry features of the MOF reduce the donor-to-acceptor singlet transfer efficiency to less than 36% compared to around 96% in the control sample, where the relative orientation of the donor and acceptor chromophores cannot be controlled.