Efficient solar energy conversion is an enormous scientific and technological challenge within synthetic materials.  The salient structural features of metal-organic frameworks including the long-range regular crystalline structure and open pore network present significant advantages for artificial photosynthesis over traditional small molecule mimics. MOFs present a promising platform by which to achieve controlled long-range charge separation upon photo-excitation and ultimately develop highly efficient light-driven catalysts for artificial photosynthesis. Towards these goals, we have developed a new two-dimensional framework structure which couples redox-active Ru3-�3-oxo clusters with Co3-carboxylate nodes (Figure) through isonicotinic acid. The Co3 nodes possess significant structural characteristics which prompt interest as an active catalytic site.  The edge and center Co sites are bridged by a carboxylate oxygen and separated by 3.49�, structurally similar to natural metal-metal enzyme sites. Additionally, two labile water molecules are bound cis to one another at the Co(II) edge sites, which upon removal, present open metal sites for substrate binding.  We will discuss this structure and others with an emphasis on the relevant structural and electronic attributes for photocatalytic applications.

Redox-active MOF with bio-mimetic cobalt nodes: Toward artificial photosynthesis in framework architectures

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.