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Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films.


ABSTRACT: Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts. Films are grown by sequential deposition of cationic Zr-based porous coordination cages and anionic Mn porphyrins. Photolysis facilitates the efficient reduction of Mn(III) sites to Mn(II) sites, which can be observed in real-time by transmission UV-vis spectroscopy. Film porosity enables substrate access to the Mn(II) sites and facilitates reversible O2 activation in the solid state. These results establish optically transparent, porous salt thin films as versatile platforms for solid-state photochemistry and in operando spectroscopy.

SUBMITTER: Sur A 

PROVIDER: S-EPMC10863064 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature

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Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films.

Sur Aishanee A   Simmons Joe D JD   Ezazi Andrew A AA   Korman Kyle J KJ   Sarkar Subham S   Iverson Ethan T ET   Bloch Eric D ED   Powers David C DC  

Journal of the American Chemical Society 20231108 46


Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts.  ...[more]

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