Photosynthesis is a complex combination of light harvesting arrays, redox shuttles, and catalytic centers that work in concert to oxidize water and reduce CO2 to sugars utilizing solar energy. Porous coordination networks (PCNs) are an attractive framework to design supramolecular systems that mimic natural assemblies. The synthetic diversity of PCNs enables key properties such as energy transfer efficiency, electron transport rates, and catalytic activity to be tuned through systematic variation. Herein, we investigate both homo-resonance energy transfer and catalytic activity in PCN thin films. The study of homo-RET has enabled the characterization of the solvent environment within PCNs and comparison of energy transfer rates to both powder PCNs and molecular systems. In accordance with literature reports, PCNs exhibit enhanced rates of energy transfer. The mechanism of electron transport through PCNs has also been investigated. Similar to redox polymers, electron transport occurs via a redox hopping mechanism. Insight into how to control the rate of redox hopping is provided and examples of water oxidation and CO2/H+ reduction discussed.

Controlling electron transport properties in PCNs for solar water splitting

248th National Meeting (2014)

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