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  1. Abstract

    Traditional MOF e‐CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi‐electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e‐CRR systems, CoPc@NU‐1000 and TPP(Co)@NU‐1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU‐1000 MOF. For CoPc@NU‐1000, the e‐CRR responsive CoI/0potential is close to that of NU‐1000 reduction compared to the TPP(Co)@NU‐1000. Efficient charge delivery, defined by a higher diffusion (Dhop=4.1×10−12 cm2 s−1) and low charge‐transport resistance (=59.5 Ω) in CoPC@NU‐1000 led FECO=80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FECO=24 % (Dhop=1.4×10−12 cm2 s−1and=91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.

     
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  2. Abstract

    Charge‐transfer excited state (CTES) defines the ability to split photon energy into work producing redox equivalents suitable for photocatalysis. Here, we report inter‐net CTES formation within a two‐fold catenated crystalline metal–organic framework (MOF), constructed with two linkers, N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide (DPNDI) and 2,6‐dicarboxynaphthalene (NDC). The structural flexibility puts two complementary linkers from two nets in a proximal position to interact strongly. Supported by the electrochemical and steady‐state electronic spectroscopic data, this ground‐state interaction facilitates forming CTES that can be populated by direct excitation. We map the dynamics of the CTES which persists over a few nanoseconds and highlight the utilities of such relatively long‐lived CTES as enhanced conductivity of the MOF under light over that measured in dark and as a proof‐of‐the‐principle test, photo‐reduction of methyl viologen under white light.

     
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  3. Abstract

    Metalorganic frameworks (MOFs) are widely studied molecular assemblies that have demonstrated promise for a range of potential applications. Given the unique and well-established photophysical and electrochemical properties of porphyrins, porphyrin-based MOFs are emerging as promising candidates for energy harvesting and conversion applications. Here we discuss the physical properties of porphyrin-based MOFs, highlighting the evolution of various optical and electronic features as a function of their modular framework structures and compositional variations.

     
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  4. Free, publicly-accessible full text available June 14, 2024
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