Symmetry-Breaking Charge Transfer in Metal–Organic Frameworks

High quantum-yield charge carrier generation from the initially prepared excitons defines a key step in the light-harvesting and conversion scheme. Photoinduced charge transfer in molecular electron donor–acceptor assemblies is driven by a sizable ΔG0, which compromises the potential of the generated carriers. Reminiscent of the special pair at the reaction center of the natural light-harvesting complex, symmetry-breaking charge transfer (SBCT) within a pair of identical struts of metal−organic framework (MOF) will facilitate the efficient generation of long-lived charge carriers with maximized potentials without incorporating any foreign redox species. We report SBCT in pyrene-based zirconium metal–organic framework (MOF) NU-1000 that leads to efficient generation of radical ions in a polar solvent and bound CT states in a low-polar solvent. The probe unveils the role of the low-lying non-Franck–Condon excitonic states as intermediates in the formation of the SBCT state from the initially prepared Franck–Condon S1 states. Ultrafast and transient spectroscopy─probed over 200 fs-30 μs time scale─evinces a kSBCT = (110 ps)−1 in polar media (εs = 37.5) forming solvated radical ions with recombination rate kCR = (∼45 ns)−1. A slower rate with kSBCT = (203 ps)−1 was recorded in low-polar (εs = 7.0) solvent manifesting a bound [TBAPy•+ TBAPy•–] state with kCR ≈ (17 μs)−1. This discovery, along with other unique photophysical features relevant to light harvesting, should define a MOF-based platform for developing heterogeneous artificial photon energy conversion systems.