Decoding Antenna Behavior in Metal—Organic Frameworks

Abstract Metal–organic frameworks (MOFs) define a solid‐state platform for developing artificial photosystems. Efficient anisotropic exciton migrations in these frameworks entail “antenna behavior” that can power up the distal interior reaction centers (RC), driving charge separation between donor‐acceptor pairs. Reminiscent of the natural light‐harvesting complex, such processes can achieve high quantum yield by exploiting the vast interior surface of the porous crystallites. It is important to understand the optimum positioning of the RC site relative to the anisotropic exciton migration path within these frameworks. The efficiency of such antenna behavior is probed here through Stern–Volmer (SV) type analysis with a series of node‐anchored redox quenchers, ferrocene‐carboxylate, ferrocene acetate, and dinitrobenzoate. Decoding various intrinsic processes, this work constructs a revised SV formalism in solid assembly that hosts ultrafast anisotropic exciton migration to account for the intrinsic exciton hopping rate from the extrinsic electron transfer rate, and the dimension of effective quenching. This transformative understanding can be applied to other relevant solid‐state assemblies.