Catalytically Active Site Mapping Realized through Energy Transfer Modeling

The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host‐guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal‐organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host‐guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host‐guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.