Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films
Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films
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DOI：
10.1021/jacs.3c09188
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发表时间：
2023-11-08
影响因子：
15
通讯作者：
Powers，David C.
中科院分区：
文献类型：
--
作者：
Sur，Aishanee;Simmons，Joe D.;Powers，David C.
合成多孔材料作为固态化学的平台和设计非均相催化剂继续获得关注。然而，在光化学和荧光光谱中的应用受到由于样品微晶度引起的光散射和由内滤光器效应引起的光穿透性差而导致的光捕获效率差的困扰。在这里，我们展示了光学透明的，光化学活性的多孔盐薄膜的逐层生长。薄膜生长的顺序沉积的阳离子锆基多孔配位笼和阴离子锰卟啉。光解促进Mn（III）位点到Mn（II）位点的有效还原，这可以通过透射UV-vis光谱实时观察。膜的孔隙率使基板访问的Mn（II）的网站，并促进可逆的O2在固态激活。这些结果建立了光学透明，多孔盐薄膜作为多功能的平台，固态光化学和opandoscopics.com。
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 O2activation in the solid state. These results establish optically transparent, porous salt thin films as versatile platforms for solid-state photochemistry andin operandospectroscopy.