Journal
INORGANIC CHEMISTRY
Volume 52, Issue 24, Pages 13833-13848Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic402236f
Keywords
-
Categories
Funding
- Searle Scholars Program
- NSF CAREER Grant [CHE-1151918]
- NIH [R01 GM102687A]
- Sandia Campus Executive Fellowship
- NSF
- California Institute of Technology
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1151918] Funding Source: National Science Foundation
Ask authors/readers for more resources
Artificial photosynthesis has emerged as an important strategy toward clean and renewable fuels. Catalytic oxidation of water to 02 remains a significant challenge in this context. A mechanistic understanding of currently known heterogeneous and biological catalysts at a molecular level is highly desirable for fundamental reasons as well as for the rational design of practical catalysts. This Award Article discusses recent efforts in synthesizing structural models of the oxygen-evolving complex of photosystem II. These structural motifs are also related to heterogeneous mixed-metal oxide catalysts. A stepwise synthetic methodology was developed toward achieving the structural complexity of the targeted active sites. A geometrically restricted multinucleating ligand, but with labile coordination modes, was employed for the synthesis of low-oxidation-state trimetallic species. These precursors were elaborated to site-differentiated tetrametallic complexes in high oxidation states. This methodology has allowed for structure reactivity studies that have offered insight into the effects of different components of the clusters. Mechanistic aspects of oxygen-atom transfer and incorporation from water have been interrogated. Significantly, a large and systematic effect of redox-inactive metals on the redox properties of these clusters was discovered. With the pK(a) value of the redox-inactive metal aqua complex as a measure of the Lewis acidity, structurally analogous clusters display a linear dependence between the reduction potential and acidity; each pKa unit shifts the potential by ca. 90 mV. Implications for the function of the biological and heterogeneous catalysts are discussed.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available