Gillmore Research Group
Students have the opportunity to join a thriving externally funded organic photochemistry research group at Hope College, with a primary focus on incorporating undergraduate students into all aspects of the research endeavor.
Organic Photochemistry For Materials Applications
Teaching Old Photochromes New Tricks
Student collaborators gain familiarity with organic synthesis, photochemistry, electrochemistry, reactive (radical and ion radical) intermediates, polymers and materials research. Together, we develop syntheses of novel organic photochromes which we apply to a range of different applications based on more than just their changing colors.
Photochromic organic molecules are compounds that undergo a reversible photochemical rearrangement from a short wavelength (SW) form to a long wavelength (LW) form, with reversion occurring thermally, photochemically or both. The vast majority of organic photochromes have been investigated for applications in ophthalmic lenses (e.g., Transitions® lenses), novelty items or data storage applications all related to their color change. Studies of the spectral changes, molar absorptivity, reversibility and fatigue resistance predominate. Exploration of other dynamic properties of photochromic compounds has been far more limited. In the Gillmore Research Group at Hope College, we attempt to make use of the changes in shape and electronics that accompany the color change of a photochrome.
We spent more than a decade focusing primarily on photochromes from the perimidinespirocyclohexadienone family. These were prepared and studied as potential "photochromic photooxidants", where the electronic changes between SW and LW affect the ability of these dyes to initiate electron transfer reactions. This can add an additional level of gating, or control, to photoinduced electron transfer processes that can be applicable to either microfabrication or photoresponsive plastics for data storage or optical waveguiding applications.
More recently the Gillmore Group is also investigating a newly reported family of BF2-coordinated azo dyes, primarily for their change in shape, rather than color. These dyes absorb at significantly longer wavelengths than conventional azo dyes. In this nascent project, the Gillmore group is working to install synthetic handles on these dyes which others have developed, so that, together with the group of Professor Matthew Smith in the Hope College Department of Engineering,
we might incorporate them into polymeric materials. In polymer networks, if properly
ordered, it is possible to couple the molecular shape change of an azo dye to bulk
shape change of the material. These are known as photomechanical materials (PMMs),
which expand, contract, or bend in response to light. PMMs have applicability to a
variety of wireless actuators. Moving from the UV to blue-green absorbance of conventional
azo dyes to the red or even near-infrared absorbance of these BF2-coordinated azo dyes will make PMMs more relevant to biological applications while
decreasing competitive absorption by other device components and minimizing photodegradation
of materials. Students on this project make, purify and characterize a range of dyes,
monomers and model compounds, as well as ultimately polymers. We study the photochromic
and eventually the photomechanical properties of the dye monomers and polymers. A
recently funded grant from the ACS PRF will allow us to take a step back to study
these novel BF2-coordinated azo dyes at a much more fundamental level, exploring the breadth of substitutions
possible and the level of tuning of the absorbance spectra that can be achieved.
Finally, the Gillmore group also applies computational modeling to help us understand the systems we study. For instance, we have developed methods to allow accurate and efficient prediction of redox properties relevant not only to our photochromic photooxidants project, but also to the energy storage projects of collaborators at the MSU Bioeconomy Institute's Organic Energy storage lab. Computations also help us understand chemical reactivity, evaluate mechanisms, and predict spectroscopic properties of our dyes.
All students in the Gillmore Group must receive departmental safety training as well as group-specific safety training at least annually, and agree to abide by the Gillmore Group Laboratory Working Agreement.
Student Researchers Wanted
The Gillmore Group is currently rebuilding after a sabbatical leave and the receipt of a new grant. New projects in organic synthesis are available to those who are taking or have completed CHEM 255, Organic I lab, while a computational project is available to well organized students with good MS Excel skills and at least GenChem I experience (AP Chem, CHEM 125 or 131). Please email to set up a meeting with Professor Gillmore to discuss opportunities in the Gillmore Group!
A. Paul Schaap Science Center35 East 12th StreetRoom 3101Holland, MI 49423