Assistant Professor – Organic Synthesis & Materials Chemistry
Research and/or Creative Works
As the world’s population (and concomitant industrialization) continues to expand, there is a growing need for low cost, “clean” sources of energy production. When compared to the most common energy sources - which are heavily reliant on fossil fuels and a major source of greenhouse gases - solar energy remains a virtually untapped renewable resource. Though organic electronic devices do not currently have the high performance characteristic of their inorganic counterparts, advantages associated with their high flexibility, cheap and easy processing, and the ease of chemical modification to fine-tune their properties make such devices a viable and cost-effective alternative. My research group is focused on developing both novel organic materials to be used in organic electronic devices and new methodologies to enhance the properties of existing materials. The majority of the research in my group focuses heavily on organic synthesis, but students also have the opportunity to gain experience in polymer chemistry, organometallic chemistry, and device fabrication and testing.
One of the primary interests in my group is novel electron-rich polycyclic aromatic hydrocarbons (PAHs) that distort from planarity - either due to steric effects or the formation of strained bonds. Due to their tendency to form energetically-favored columnar superstructures and their shape-defined affinity to interact with electron-acceptors such as fullerenes, there is tremendous potential for the implementation of such molecules into organic field effect transistors (OFETs) and organic photovoltaic devices (OPVs). Currently, we are targeting circulene and larger members of the circulene family as these molecules are predicted to maintain aromaticity despite distorting from planarity to adopt a unique saddle shape.
Another research interest in my group is conjugated polymers. Examples of these compounds range from poly(3-hexylthiophene), which is widely considered to be the benchmark material for hole-conduction in OPVs, to poly(p-phenylene vinylene) which was the first conjugated polymer to be incorporated into a commercial light emitting diode. Synthesizing conjugated polymers by current methods often leads to either defect sites in the polymer, which reduces the utility of the compound, or solubility issues that lead to polymers with low molecular weights. By utilizing 3-dimensional coordination polymers as templates, we are developing methods to overcome the limitations in the synthesis of conjugated polymers. Fueled by the assumption that prepaying the energetic cost of assembly by formation of the organometallic template will result in artificially high polymerization efficiencies, we envision the ability to generate highly ordered, high molecular weight conjugated polymers.
My group is also interested in the study and synthesis of carbon nanotubes (CNTs). The utility of CNTs in commercial applications has been severely limited by the ability to control the size, shape, and conductivity of the tubes during growth. We are currently synthesizing small portions of specific tube chiralities with the goal of using these compounds as seeds for CNT growth. Studying the photophysical properties of these tube fragments will also provide insight into the origin of the magnificent properties associated with CNTs.
Lilly, G. D.; Whalley, A. C.; Grunder, S.; Valente, C.; Frederick, M. T.; Stoddart, J. F.; Weiss, E. A., Switchable photoconductivity of quantum dot films using cross-linking ligands with light-sensitive structures, J. Mater. Chem. 2011, 21, 11492-11497. Cover Article
Beuerle, F.; Herrmann, C.; Whalley, A. C.; Valente, C.; Gamburd, A.; Ratner, M. A.; Stoddart, J. F., Optical and vibrational properties of toroidal carbon nanotubes, Chem. Eur. J. 2011, 17, 3868-3875. Cover Article
Boyle, M. M.; Smaldone, R. A.; Whalley, A. C.; Ambrogio, M. W.; Botros, Y. Y.; Stoddart, J. F., Mechanised materials, Chem. Sci. 2011, 2, 204-210. Cover Article
Whalley, A. C..; Plunkett, K. N.; Gorodetsky, A.; Schenck, C. L.; Chiu, C.-Y.; Steigerwald, M. L.; Nuckolls, C. N., Bending contorted hexabenzocoronene into a bowl, Chem. Sci. 2011, 2, 132-135.
Kamenetska, M.; Quek, S. Y.; Whalley, A. C.; Steigerwald, M. L.; Choi, H. J.; Louie, S. G.; Nuckolls, C.; Hybertsen, M. S.; Neaton, J. B.; Venkataraman, L., Conductance and geometry of pyridine-linked single molecule junctions, J. Am. Chem. Soc., 2010, 132, 6817-6821.
Plunkett, K. N.; Godula, K.; Nuckolls, C.; Tremblay, N.; Whalley, A. C.; Xiao, S., Expeditious synthesis of contorted hexabenzocoronenes, Org. Lett. 2009, 11, 2225-2228.
Areas of Expertise and/or Research
organic chemistry, materials chemistry and science
- M.A., Columbia University, NY, NY, 2006
- Ph.D., Columbia University, NY, NY, 2009
- Postdoctoral fellowship, Northwestern University, Chicago, IL, 2009-2012
- (802) 656-8246