个人简介

B.S., 1967, Dickinson College Ph.D., 1972, Massachusetts Institute of Technology Visiting Fellow, 1985, 1994, Australian National University USC Educational Foundation Research Award for Science, Mathematics, and Engineering, 1995; Michael J. Mungo Award for Excellence in Undergraduate Teaching, 1995; Amoco Foundation Outstanding Teaching Award, 1996; Carolina Trustee Professorship, 2000; Michael J. Mungo Award for Excellence in Graduate Teaching, 2003; South Carolina Governor's Award for Excellence in Scientific Research, 2007; University of South Carolina Educational Foundation Outstanding Service Award, 2008; American Chemical Society Outstanding South Carolina Chemist of the Year, 2008; Fellow of the American Association for the Advancement of Science, 2011; Charles H. Stone Award, Charlotte/Piedmont Section of the American Chemical Society, 2011; Southern Chemist Award, Memphis Section of the American Chemical Society, 2013.

研究领域

Inorganic

Inorganic chemistry. Synthesis of third generation poly(pyrazolyl)methane and poly(pyrazolyl)borate ligands and ligands containing aromatic groups that form strong π-π stacking interactions; preparation of metal complexes of these ligands that have unusual magnetic and structural properties. Our group is the leader worldwide in the development of the chemistry of tris(pyrazolyl)methane ligands. These ligands, the neutral analogs of the extensively investigated, isoelectronic tris(pyrazolyl)borate ligands, were not studied extensively prior to our work because they were difficult to prepare. We have now dramatically improved these preparations making the whole family of HC(3-Rpz)3 (pz = pyrazolyl ring;R = Ph, Pri, But) ligands and HC(3,5-Me2pz)3 readily available for the first time. We have functionalized these new ligands to prepared a number of new polytopic ligands (those with multiple pol(pyrazolyl)methane units in a single molecule), a development that represent the first major effort to prepare “third generation” poly(pyrazolyl)methane ligands. Third generation ligands are specifically functionalized at the non-coordinating, “back” position, distal from the metal environment, for the purpose of appending new/desired functionality into the systems under study while not impacting the direct environment about the metal. We have developed unusual chemistry of many different metal system with these ligands. A particularly exciting example is the reaction of M(BF4)2 compounds with Lm resulting in fluoride abstraction leading to the complexes [M2(u-F)(u- Lm)2](BF4)3 (see below for M = Fe structure) in which a single fluoride ligand and two Lm molecules bridge the two metal centers. The M = Fe complex shows weakly antiferromagnetic behavior. In a separate project we have used tris(pyrazolyl)methane ligands to prepare new iron(II) complexes that show very unusual spin properties. The complex {[HC(3,5-Me2pz)3]2Fe}(BF4)2 is fully high spin from 350 K to 206 K then undergoes an abrupt spin change to a mixture of high and low spin forms, an unprecedented result. It also undergoes a solid-state phase change at 206 K, a change we have observed for other analogous complexes of first row metals showing that the phase change drives the spin-state change. In recent work we are studying the effects of controlling spin-crossover effects by manipulating the supramolecular structures of the compounds. We have synthesized a new family of “third generation” poly(pyrazolyl)borate ligands. Using these ligands we have been able to show that subtle changes in either molecular or supramolecular structure can greatly influence the spin-crossover behavior of iron(II) complexes. The figure shows the three dimensional structure of one polymorph of Fe[(p-IC6H4)B(3-Mepz)3]2 where the highly organized structure prevents the molecules from undergoing spin crossover at low temperature. Incorporating the 1,8-naphthalimide group into bis(pyrazolyl)-methane ligands allows the asscoiation of their metal complexes into directionally ordered dimers by strong π-π stacking interactions in both solution and solid-state, as pictured. The incorporation of this π-bonding group into acetate ligands leads to the formation of paddlewheel metalladimers with very unusual supramolecular structures held together by non-covalent forces, as pictured.

近期论文

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Reger, D. L., Pascui, A. E., Foley, E. A., Smith, M. D., Jezierska, J., and Ozarowski, A. “Dinuclear Metallacycles with Single M-O(H)-M Bridges [M = Fe(II), Co(II), Ni(II), Cu(II)]: Effects of Large Bridging Angles on Structure and Antiferromagnetic Superexchange Interactions,” Inorg. Chem. 2014, 53, 1975-1988 Reger, D. L., Pascui, A. E., Pellechia, J., Smith, M. D., Jezierska, J., and Ozarowski, A. “Hydroxide Bridged Cubane Complexes of Nickel(II) and Cadmium(II): Magnetic, EPR and Unusual Dynamic Properties,” Inorg. Chem. 2014, 53, 4325-4339 Reger, D. L., Leitner, A. P., Smith, M. D., Tran, T. T., Halasyamani, P.S., “Homochiral Helical Metal-Organic Frameworks of Group 1 Metals,” Inorg. Chem. 2013, 52, 10041-10051 Reger, D. L., Pascui, A. E., Pellechia, P. J., Smith, M.D. “Zinc(II) and Cadmium(II) Monohydroxide Bridged, Dinuclear Metallacycles: A Unique Case of Concerted Double Berry Pseudorotation,” Inorg. Chem. 2013, 52, 11638-11649 Reger, D. L., Pascui, A. E., Pellechia, P. J., Ozarowski, A. “NMR Investigations of Dinuclear, Single Anion Bridged Copper(II) Metallacycles: Structure and Antiferromagnetic Behavior in Solution,” Inorg. Chem. 2013, 52, 12741-12748 Reger, D. L., Pascui, A. E., Smith, M. D., Jezierska, J., Ozarowski, A. ""Halide and Hydroxide Linearly Bridged Bimetallic Copper(II) Complexes: Trends in Strong Antiferromagnetic Superexchange Interactions,” Inorg. Chem. 2012, 51, 7966–7968 Reger, D. L., Leitner, A. P., Smith, M. D. ""Homochiral Helical Main Group Metal-Organic Frameworks: Potassium,"" Inorg. Chem. 2012, 51, 10071-10073 Reger, D. L., Pascui, A. E., Smith, M. D., Jezierska, J., Ozarowski, A. ""Dinuclear Complexes Containing Linear M-F-M (M = Mn(II), Fe(II), Co(II), Ni(II), Zn(II), Cd(II)) Bridges: Trends in Structures, Antiferromagnetic Superexchange Interactions and Spectroscopic Properties,"" Inorg. Chem. 2012, 51, 11820-11836 Reger, D. L., Debreczeni, A., Smith, M.D. “Homochiral, Supramolecular Frameworks Built from a Zinc(II) Tetramer or Cadmium(II) Dimer Containing Enantiopure Carboxylate Ligand Functionalized with a Strong π-π Stacking Stacking Synthon,” Eur. J. Inorg. Chem. 2012, 712-719 Reger, D. L., Debreczeni, A., Smith, M. D., Jezierska, J., Ozarowski, A. “Copper(II) Carboxylate Dimers Prepared from Ligands Designed to Form a Robust π-π Stacking Stacking Synthon: Supramolecular Structures and Molecular Properties,” Inorg. Chem. 2012, 51, 1068-1083 Reger, D. L. , Debreczeni, A., Smith, M. D. “Zinc Paddlewheel Dimers Containing a Strong π-π Stacking Supramolecular Synthon: Designed Single-Crystal to Single-Crystal Phase Changes and Gas/Solid Guest Exchange,” Inorg. Chem. 2011, 50, 11754-11764 Reger, D. L. , Horger, J. J., Debreczeni, A., Smith, M. D. “Syntheses and Characterization of Copper(II) Carboxylate Dimers formed from Enantiopure Ligands Containing a Strong π-π Stacking Synthon: Enantioselective Single-Crystal to Single-Crystal Gas/Solid-Mediated Transformations,” Inorg. Chem. 2011, 50, 10225-10240