Our research is concerned with the chemistry of both organic and organometallic polyfunctional Lewis acids. While an important component of our work deals with the synthesis of new examples of such polyfunctional Lewis acids, it is our ultimate intent to harness and utilize the cooperative effects occurring in such systems for the discovery of unusual structures, bonding modes, supramolecules and reactivities. Our research efforts present important ramifications in the domain of molecular recognition, supramolecular materials and catalysis.
Synthesis: Organic and organometallic synthesis lies at the focal point of our program. We strive to discover high yield synthetic routes for the preparation of both organic and organometallic polyfunctional Lewis acids. These efforts have allowed us to prepare a variety of bidentate and tridentate Lewis acids in which the electrophilic sites are simple carbocations or main-group elements such as mercury(II) and boron(III).
Bonding: In an effort to broaden our fundamental understanding of bonding interactions, we study atypical bonding situations that might arise in the chemistry of polyfunctional Lewis acids. While we have been interested in the formation of radicals featuring one-electron s-bonds, some of our current efforts are devoted to the synthesis of fluoronium ions.
Molecular recognition: Some of these polyfunctional Lewis acids act as polytopic receptors for anions. The significance of this research relates to the discovery of new molecular recognition units for sensory application. For example, we have recently demonstrated that boron-based bidentate Lewis acids can be used as selective colorimetric sensors for fluoride ions. Taking into account the importance of fluoride in the treatment of osteoporosis and in dental care, such sensors may find biomedical applications.
Supramolecular materials: In addition to discovering receptors for small organic molecules including diazines, ketones, aldehydes, oxiranes, and phosphonates, we have also found that trimeric perfluoro-ortho-phenylene mercury, a tridentate Lewis acid, is able to complex many arenes including benzene, naphthalene, biphenyl and pyrene. The resulting adducts form unusual supramolecular binary stacks. In addition, these adducts display unique luminescent properties which make them useful materials for organic light emitting diodes (OLED). Some of these adducts form microporous solids used for gas storage.
Neutral and Cationic Lewis acids in molecular and supramolecular chemistry.
Ke, I.-S.; Jones, J. S.; Gabbaï, F. P. "Anion-Controlled Switching of an X-Ligand into a Z-Ligand: Coordination Non-innocence of a Stiboranyl Ligand" Angew. Chem. Int. Ed. 2014, 53, 2633-2637.
Hirai, M.; Gabbaï, F. P. "Lewis acidic stiborafluorenes for the fluorescence turn-on sensing of fluoride in drinking water at ppm concentrations" Chem. Sci. 2014, 5, 1886-1893.
Lin, T.-P.; Gabbaï, F. P. "Telluronium Ions as -Acceptor Ligands" Angew. Chem. Int. Ed. 2013, 52, 3864-3868.
Liu, S.; Lin, T.-P.; Li, D.; Leamer, L.; Shan, H.; Li, Z.; Gabbaï, F. P.; Conti, P. S. "Lewis Acid-Assisted Isotopic 18F-19F Exchange in BODIPY Dyes: Facile Generation of Positron Emission Tomography/Fluorescence Dual Modality Agents for Tumor Imaging" Theranostics 2013, 3, 181-189.
Zhao, H.; Leamer, L. A.; Gabbaï, F. P. "Anion capture and sensing with cationic boranes: on the synergy of Coulombic effects and onium ion-centred Lewis acidity" Dalton Trans. 2013, 42, 8164-8178.
Fleischmann, M.; Heindl, C.; Seidl, M.; Balázs, G.; Virovets, A. V.; Peresypkina, E. V.; Tsunoda, M.; Gabbaï, F. P.; Scheer, M. "Discrete and Extended Supersandwich Structures Based on Weak Interactions between Phosphorus and Mercury" Angew. Chem. Int. Ed. 2012, 51, 9918-9921.
Ke, I.-S.; Myahkostupov, M.; Castellano, F. N.; Gabbaï, F. P. "Stibonium Ions for the Fluorescence Turn-On Sensing of F- in Drinking Water at Parts per Million Concentrations" J. Am. Chem. Soc. 2012, 134, 15309-15311.
Li, Z.; Chansaenpak, K.; Liu, S.; Wade, C. R.; Zhao, H.; Conti, P. S.; Gabbaï, F. P. "Harvesting [18F]-fluoride ions in water via direct 18F-19F isotopic exchange: Radiofluorination of zwitterionic aryltrifluoroborates and in vivo stability studies" Med. Chem. Comm. 2012, 3, 1305-1308.
Lin, T.-P.; Ke, I.-S.; Gabbaï, F. P. " -Accepting Properties of a Chlorobismuthine Ligand" Angew. Chem. Int. Ed. 2012, 51, 4985-4988.
Lin, T.-P.; Nelson, R. C.; Wu, T.; Miller, J. T.; Gabbaï, F. P. "Lewis acid enhancement by juxtaposition with an onium ion: the case of a mercury stibonium complex" Chem. Sci. 2012, 3, 1128-1136.
Wade, C. R.; Ke, I.-S.; Gabbaï, F. P. "Sensing of Aqueous Fluoride Anions by Cationic Stibine-Palladium Complexes" Angew. Chem. Int. Ed. 2012, 51, 478-481.
Wade, C. R.; Gabbaï , F. P. "Fluoride Anion Chelation by a Bidentate Stibonium-Borane Lewis Acid" Organometallics 2011, 30, 4479-4481.
Wade, C. R.; Gabbaï, F. P. "Two-Electron Redox Chemistry and Reversible Umpolung of a Gold-Antimony Bond" Angew. Chem. Int. Ed. 2011, 50, 7369-7372.
Zhao, H.; Gabbaï, F. P. "A bidentate Lewis acid with a telluronium ion as an anion-binding site" Nat. Chem. 2010, 2, 984-990.
Lin, T.-P.; Wade, C. R.; Pérez, L. M.; Gabbaï, F. P. "A Mercury→Antimony Interaction" Angew. Chem. Int. Ed. 2010, 49, 6357-6360.
Wade, C. R.; Broomsgrove, A. E. J.; Aldridge, S.; Gabbaï, F. P. "Fluoride Ion Complexation and Sensing Using Organoboron Compounds" Chem. Rev. 2010, 110, 3958-3984.