Dr. Stephen DiMagno, Willa Cather Professor
University of Nebraska-Lincoln
818 Hamilton Hall
Lincoln, Nebraska 68588-0304
Among first to earn NSF I-Corps grant (Office of Research Video)
The research program of Stephen DiMagno concerns the development of new robust macrocyclic ligands for a variety of catalytic and photochemical studies. The principal thrust of this work is directed toward the synthesis of new types of porphyrins and porphyrinoid pigments that are resistant to chemical and photochemical oxidation, and their incorporation into polymeric films and glasses. Enhanced chemical stabilities (as well as solubility, volatility and processibility) are imparted to the porphyrin ligands by fluorine substitution, either directly on the macrocycle periphery or on the side-chains. This strategy has led to the design and synthesis of two new classes of heavily fluorinated compounds, meso-perfluoroalkylated porphyrins such as 5,10,15,20-tetrakis (heptafluoropropyl) porphyrin, and beta-octafluorinated derivatives represented by 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis (pentafluorophenyl) porphyrin. These ligands have been shown to promote alkane functionalization chemistry in rhodium derivatives, and have proven to be useful probes for delineating stereoelectronic effects in porphyrins generally.
This work is supported by DARPA and by the Nebraska Center for Materials and Nanoscience.
Fluorinated Porphyrins and Corroles: Synthesis, Electrochemistry, and Applications, J. C. Biffinger, H. Sun, S. G. DiMagno, Fluorine in Heterocyclic Chemistry. V. Nenajdenko, Ed., 2013, Springer.
Replacement of BF4- by PF6- makes Selectfluor greener, Z. Jina, B. Xua, S. G. DiMagno, G. B. Hammond, J. Fluor. Chem. 2012, 143, 226–230 (DOI: 10.1016/j.jfluchem.2012.05.010)
Unprecedented Directing Group Ability of Cyclophanes in Arene Fluorinations with Diaryliodonium Salts, J. W. Graskemper, B. Wang, L. Qin, K. D. Neumann, S. G. DiMagno, Org. Lett. 2011, 13, 3158-3161 (DOI: 10.1021/ol201080c).
Ligand Fluorination to Optimize Preferential Oxidation (PROX) of Carbon Monoxide by Water-Soluble Rhodium Porphyrins, J. C. Biffinger, S. Uppaluri, H. Sun, and S. G. DiMagno, ACS Catalysis, 2011, 1, 764–771. (DOI: 10.1021/cs2001187.)
Sun, HR (Sun, Haoran); Wang, BJ (Wang, Bijia); DiMagno, SG (DiMagno, Stephen G.),A Method for Detecting Water in Organic Solvents, ORGANIC LETTERS, 10 (20): 4413-4416 Oct 16 2008
Sun, H (Sun, Haoran); Wang, BJ (Wang, Bijia); Dimagno, SG (Dimagno, Stephen G.), Ion pairing of "weakly-coordinated" fluoride salts, CHIMICA OGGI-CHEMISTRY TODAY, 26 (3): 4-6 Suppl. 1 May-Jun 2008
Sun, HR (Sun, Haoran); DiMagno, SG (DiMagno, Stephen G.), Competitive demethylation and substitution in N,N,N-trimethylanilinium fluorides, JOURNAL OF FLUORINE CHEMISTRY, 128 (7): 806-812 Sp. Iss. SI Jul 2007
Sun, H (Sun, Haoran); DiMagno, SG (DiMagno, Stephen G.), Fluoride relay: a new concept for the rapid preparation of anhydrous nucleophilic fluoride salts from KF, CHEMICAL COMMUNICATIONS, (5): 528-529 2007
Crapster, JA (Crapster, John Aaron); Koch, AS (Koch, Andrew Scott); DiMagno, SG (DiMagno, Stephen G.), Synthesis of benzyltributylammonium fluoride and its use as a novel anhydrous fluorinating salt, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 231: - 531-CHED Mar 26 2006
DiMagno, SG (DiMagno, Stephen G.); Sun, HR (Sun, Haoran), The strength of weak interactions: Aromatic fluorine in drug design, CURRENT TOPICS IN MEDICINAL CHEMISTRY, 6 (14): 1473-1482 2006.
H. Sun, R. Xue, A. P. Nelson, J. Redepenning and S. G. DiMagno, Inorg. Chem. 42, 4507-4509 (2003).
H. Sun, V. V. Smirnov and S. G. DiMagno, Inorg. Chem. 42, 6032-6040, (2003).
J. C. Biffinger, H. Sun, A. P. Nelson and S. G. DiMagno, Org. Biomol. Chem. 1, 733- (2003).
- Justin Biffinger, Ph. D. (2004), now scientist at Naval Research Laboratory.
- Valeriy V. Smirnov, Ph. D. (2004), now postdoctoral fellow at Johns Hopkins University.
- Hong Woo Kim, Ph. D. (2000), now scientist at Valeant Pharmaceutical in San Diego, CA.