Robert J. Gilliard, Jr.
B.S. Clemson University, 2009
Ph.D. University of Georgia, 2014
UNCF/Merck, Ford Foundation Postdoctora Fellow, ETH Zürich and Case Western Reserve University, 2014-2017
Synthetic Chemistry: Main-Group and Organometallic Chemistry, Bond Activation and Catalysis, Hybrid Materials
The Gilliard Research Laboratory focuses its efforts on the synthesis, structure, reactivity and applications of main-group and late transition metal species. We develop novel synthetic methods to access molecules that are relevant to a wide range of energy-related problems. In many cases, the compounds of interest contain reactive or unstable components (e.g., radicals, hydrides, multiple bonds, etc.). Accordingly, we utilize various anaerobic synthetic procedures including Schlenk techniques and inert atmosphere gloveboxes.
Current research themes under investigation include:
Bond Activation and Catalysis Mediated by Main-Group Elements - we are targeting catalysts and catalyst precursors which activate relatively inert chemical bonds (e.g., C-H, N-H, Si-H), critically important processes for tackling our current energy problems. We are also concerned with the interaction of these compounds with important energy-related small molecules such as CO, CO2, and H2.
Hybrid Materials - we are developing novel hybrid inorganic-organic polymers which contain unconventional d- and p-block element components in their structure for advancements in organic light emitting diode (OLED) technologies and molecular electronics.
Heterocycles and Bioactive Organometallics - we are synthesizing novel conjugated heterocycles which contain heavier main-group elements, mimicking the structural features of bioactive transition metal species. The physio-chemistry of these new complexes will be explored for future applications in medicinal chemistry.
Wang, Guocang; Walley, Jacob E.; Dickie, Diane A.; Pan, Sudip; Frenking, Gernot; Gilliard Jr., Robert J. "A Stable, Crystalline Beryllium Radical Cation" J. Am. Chem. Soc. 2020, 142, 4560-4564. DOI: 10.1021/jacs.9b13777. *Highlighted by Chemical & Engineering News: "Beryllium Radical Cation Isolated"
Yang, W.; Krantz, K.; Freeman, Lucas A.; Dickie, Diane A.; Molino, Andrew; Wilson, David J. D.; Gilliard Jr., Robert J. "Crystalline BP-Doped Phenanthryne via Photolysis of the Elusive Boraphosphaketene" Angew. Chem. Int. Ed. 2020, 59, 3971-3975. DOI: 10.1002/anie.201916362
Yang, W.; Krantz, K.; Freeman, Lucas A.; Dickie, Diane A.; Molino, Pan S.; Frenking, G.; Andrew; Wilson, David J. D.; Gilliard Jr., Robert J. "Persistent Borafluorene Radicals" Angew. Chem. Int. Ed. 2020, 59, 3850-3854. DOI: 10.1002/anie.201909627
Yang, W.; Krantz, K.; Freeman, Lucas A.; Dickie, Diane A.; Molino, Andrew; Aishvaryadeep, K.; Wilson, David J. D.; Gilliard Jr., Robert J. "Stable Borepinium and Borafluorenium Heterocycles: A Reversible Thermochromic "Switch" Based on Boron-Oxygen Interactions" Chem.−Eur. J. 2019, 25, 12512-12516. DOI: 10.1002/chem.201903348 *Hot Paper
Wang, Guocang; Freeman, Lucas A.; Dickie, Diane A.; Mokrai, Réka; Benkő, Zoltán; Gilliard Jr., Robert J. "Isolation of a Cyclic(Alkyl)(Amino) Carbene-Bismuthinidene Mediated by a Beryllium(0) Complex" Chem.−Eur. J. 2019, 25, 4335-4339. DOI: 10.1002/chem.201900458. *Special Collection: United Nations International Year of the Periodic Table * Highlighted in ChemistryViews Magazine
Walley, Jacob E.; Breiner, Grace; Wang, Guocang; Dickie, Diane A.; Molino, Andrew; Dutton, Jason L.; Wilson, David J. D.; Gilliard Jr., Robert J. "s-Block Carbodicarbene Chemistry: C(sp3)−H Activation and Cyclization Mediated by a Beryllium Center" Chem. Commun. 2019, 55, 1967-1970. DOI: 10.1039/C8CC10022E