Materials Chemistry
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
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.
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.
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.
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.