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Materials Chemistry

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Our group is broadly interested in the applications of organic synthesis, not only in traditional areas (e.g. natural products synthesis), but also in the design of new types of materials.  Our goal is to control the shapes of new materials with the same level of precision that we exercise when controlling the stereochemical relationships in a natural products synthesis. One research focus involves the design, synthesis and studies of unnatural molecules that are analogous to metalloproteins. Recently, we have reported molecules that fold into helical structures in response to a metal. The x-ray structure is displayed. Extensive NMR studies show that the materials fold in solution as well. When the nucleating metal is copper, electrochemistry can be used turn the helicity ‘ON’ or ‘OFF’. We believe that this provide the basis for switchable NLO materials and will provide a new design for switching phases of chiral liquid crystals. These molecules will form the basis of new types of enantioselective catalysts, and they have provided insight into the mechanism of asymmetric induction with chiral salen catalysts.

   
Some recent publications in this area

Blackman, M. L.; Royzen, M.; Fox, J. M. "The Tetrazine Ligation: Fast Bioconjugation based on Inverse-electron-demand Diels-Alder Reactivity" ASAP

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Dong, Z.; Yap, G. P. A.; Fox, J. M. “trans-Cyclohexane-1,2-diamine Is a Weak Director of Absolute Helicity in Chiral Nickel-Salen Complexes” J. Am. Chem. Soc. 2007, 129, 11850-11853.

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Dong, Z.; Liu, X.; Yap, G. P. A.; Fox, J. M. “Two-Dimensional Scaffolds for the Parallel Alignment of Rod-Shaped Conjugated Molecules” J. Org. Chem.  2007, 72, 617-625.

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Dong, Z.; Karpowicz, R. J. Jr.; Bai, S.; Yap, G. P. A.; Fox, J. M. “Control of Absolute Helicity in Single-Stranded Abiotic Metallofoldamers” J. Am. Chem. Soc. 2006, 128,14242-14243.

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Zhang, F.; Bai, S.; Yap, G. P. A.; Tarwade, V.; Fox, J. M. “Abiotic Metallofoldamers as Electrochemically Responsive Molecules” J. Am. Chem. Soc. 2005, 127, 10590-10599.

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