Rhett C. Smith
Assistant Professor
Organic Materials
Phone: 864 656 6112
Office: 479 Hunter
E-mail: rhett@clemson.edu
Research Interests | Publications | How to Join the Rhett Smith Group
Dr. Smith received his B.S. (2000) from University of Toledo where he did research with Prof. Robert A. Flowers, II; and his Ph.D. (2004) from Case Western Reserve University working with Prof. John D. Protasiewicz. The title of his Ph.D. dissertation is “Studies on Low-Coordinate Phosphorus Centers and Sterically Encumbered Ligands: Structure, Reactivity, Materials, and Catalysis”. He was a National Institute of Health Postdoctoral Fellow (2004-2006) at the Massachusetts Institute of Technology in the laboratory of Prof. Stephen J. Lippard where he prepared fluorescent biosensors for neurochemical applications. His research focus includes the synthesis and applications of organic and inorganic materials for fluorescent sensing of biologically relevant agents such as neurotoxins, preparing small molecule models of enzyme active sites, and uncovering environmentally-friendly catalytic reactions.
Research Interests
The Smith group’s research is in the broad area of Organic/Inorganic Materials for catalytic, biomimetic and biosensor applications. We are currently recruiting undergraduate and graduate researchers to work in three main areas:
1. Fluorescent Sensors for Pesticides, Chemical Warefare Agents, and other Neurotoxins
Organophosphorus (OP) pesticides are pervasive in our environment. Structurally similar nerve agents pose a threat as instruments of chemical warfare or terrorism. Reliable methods for the detection of such agents is currently the subject of multiple initiatives from the NSF, DOD, and others. The Smith group will apply organic small molecules, light-harvesting polymers, and polyelectrolyte complexes to colorimetric and fluorescent detection of OP toxins for thin film and device applications.
The Smith group is interested in applications of chromophore-derivatized metal enzyme models as neurotoxin receptors for sensor applications. We will begin our workin this area by studying known OP-binding metal sites as receptors for organophosphorus neurotoxins.
2. Biomimetic Chemistry: Enzyme Models
Life depends upon the ability of an organism to carry out chemical reactions reliably, efficiently, and with specificity; such reactions are mediated by enzymes. These remarkable biochemical catalysts can accomplish an impressive range of chemical transformations under mild, physiological conditions. Metalloenzymes make use of one or more transition metal center disposed in a geometry at the active site to facilitate the binding, positioning, activation, and/or reaction of the substrate.
The Smith group is interested in modeling enzyme active sites using small molecules that are readily prepared in the laboratory. Specifically, we are targeting a number of bimetallic hydrolase models to examine the dependence of activity upon M-M distance and ligand sterics/electronics.
3. Rhodium Catalysts for Green Chemistry
Chemists rely upon late transition metal catalyzed reactions for functional group tolerant transformations under mild conditions. These reactions can be accomplished asymmetrically when chiral ligands comprise a functional module of the catalyst (subject of the 2001 Nobel Prize in Chemistry). Among late transition metal catalysts often employed in C-C bond-forming reactions, those employing palladium and rhodium have found particular success. Rhodium-catalyzed reactions can often be carried out in aqueous or biphasic systems, making them of particular interest for utility in green chemical applications.
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Publications
Smith, Rhett C.; Gleason, L. Beth; Protasiewicz, John D. “Solution and Film Photoluminescence of Mesityl-Substituted PPVs and Low Molecular Weight Models” Chemistry of Materials, 2005, submitted.
Smith, Rhett C.; Tennyson, Andrew G.; Lim, Mi Hee; Lippard, Stephen J.; “Conjugated Polymer-Based Fluorescence Turn-On Sensor for Nitric Oxide” Organic Letters, 2005, 7, 3573.
Ma, Liqinq; Smith, Rhett C.; Protasiewicz, John D. “Self-Assembled Coordination Polymers of Palladium by Ligand Rearrangement” Inorganica Chimica Acta, 2005, 358, 3478-3482.
Smith, Rhett C.; Bodner, Christina R.; Earl, Meredith; Sears, Nathaniel C.; Hill, Nicholas E.; Bishop, Lee M.; Sizemore, Nicholas; Hehemann, Dave T.; Bohn, Justin J.; Protasiewicz, John D. “Suzuki and Heck Coupling Reactions Mediated by Wide Bite Angle Diphosphine Palladium Catalysts” Journal of Organometallic Chemistry, 2004, 690, 477-481.
Smith, Rhett C.; Woloszynek, Robert A.; Rheingold, Arnold L.; Protasiewicz, John D. “Synthesis, Structure, and Reactivity of Arsanylidene-▢-phosphoranes (ArAs=PMe3) and Utility in the Preparation of a Diarsene PPV” Organometallics, 2004, 23, 5124-5126.
Smith, Rhett C.; Woloszynek, Robert A.; Chen, Weizhong; Ren, Tong; Protasiewicz, John D. “Synthesis, Structure, and Catalysis with Palladium Complexes of the Bulky (2,6-dimesitylphenyl)dimethylphosphane” Tetrahedron Letters, 2004, 45, 8327-8330.
Smith, Rhett C.; Earl, Meredith J.; Protasiewicz, John D. “Synthesis and Photoluminescence Properties of a Series of Pnictogen-Centered Chromophores” Inorganica Chimica Acta, 2004, 457, 4139-4143.
Smith, Rhett C.; Protasiewicz, John D. “Wide Bite Angle Diphosphine Ligand Based on a m-Terphenyl Scaffold” Organometallics 2004, 23, 4215-4222.
Smith, Rhett C.; Protasiewicz, John D. “Systematic Investigation of PPV Analogue Oligomers Incorporating Low-Coordinate Phosphorus Centers” European Journal of Inorganic Chemistry 2004, 5, 998.
Chen, Xufang; Smith, Rhett C.; Protasiewicz, John D. “Cycloaddition of phosphanylidene-▢-phosphoranes ArP=PMe3 and quinones to yield 1,3,2-dioxophospholanes” Chemical Communications, 2003, 146-147.
Smith, Rhett C.; Protasiewicz, John D. “Synthesis and Luminescence Properties of a series of tris-(4-styrylphenyl) Phosphorus (III) and (V) Compounds and of a [Cu(PR3)4]BF4 Complex” Dalton Transactions 2003, 24, 4738-4741.
Smith, Rhett C.; Protasiewicz, John D. “Conjugated Polymers Featuring Heavier Main Group Element Multiple Bonds: A Diphosphene-PPV” Journal of the American Chemical Society 2003, 126, 2268-2269.
Dutan, Cosmina; Shah, Shashin; Smith, Rhett C.; Choua, Sylvie; Berclaz, Theo; Geoffroy, Michel; Protasiewicz, J. D. “Sterically Encumbered Diphosphaalkenes and a Bis(diphosphene) as Potential Multiredox-Active Molecular Switches: EPR and DFT Investigations” Inorganic Chemistry 2003, 42, 6241-6251.
Smith, Rhett C.; Chen, Xufang; Protasiewicz, John D. “A Fluorescent (E)-Poly(p-phenylenephosphaalkene) Prepared by a Phospha-Wittig Reaction” Inorganic Chemistry 2003, 42, 5468-5470.
Shah, Shashin; Eichler, Barrett E.; Smith, Rhett C.; Power, Philip P.; Protasiewicz, John D. “Synthesis and Solid State Structures of Increasingly Sterically Crowded 1,4-Diiodo-2,3,5,6-Tetraarylbenzenes: A New Series of Bulky Benzenes and Aryls”, New Journal of Chemistry 2003, 27, 442-445.
Copeland, Tiffany; Shea, Michael P.; Milliken, Matt C.; Smith, Rhett C.; Protasiewicz, John D.; Simpson, M. Cather “Raman excitation profile of a sterically protected diphosphene [ArP=PAr]” Analytica Chimica Acta 2003, 496, 155-163.
Smith, Rhett C.; Shah, Shashin; Urnezius, Eugenijus; Protasiewicz, John D. “An Unusual Equilibrium Chlorine Atom Transfer Process and Its Potential for Assessment of Steric Pressure by Bulky Aryls” Journal of the American Chemical Society 2003, 25, 40-41.
Smith, Rhett C.; Ren, Tong; Protasiewicz, John D. “A Robust, Reactive, and Remarkably Simple to Prepare Sterically Encumbered m-Terphenyl Ligand” European Journal of Inorganic Chemistry 2002, 11, 2779-2783.
Smith, Rhett C.; Urnezius, Eugenijus; Lam, Kin-Chung; Rheingold, Arnold L.; Protasiewicz, John D. “Syntheses and Structural Characterizations of the Unsymmetrical Diphosphene DmpP:PMes* (Dmp = 2,6-Mes2C6H3, Mes* = 2,4,6-t-Bu3C6H2) and the Cyclotetraphosphine [DmpPPPh]2” Inorganic Chemistry 2002, 41, 5296-5299.
Smith, Rhett C.; Shah, Shashin; Protasiewicz, John D. “A Role for Free Phosphinidenes in the Reaction of Magnesium and Sterically Encumbered ArPCl2 in Solution at Room Temperature” Journal of Organometallic Chemistry 2002, 646, 255-261.
Shah, Shashin; Simpson, M. Cather; Smith, Rhett C.; Protasiewicz, John D. “Three Different Fates for Phosphinidenes Generated by Photocleavage of Phospha-Wittig Reagents ArP=PMe3” Journal of the American Chemical Society 2001, 23, 6925-6926.
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How to Join the Rhett Smith Group
Undergraduate Researchers: Send me an e-mail including a bit about yourself and the project area(s) in which you are interested, and we can set up an appointment. Undergraduates of all levels are welcome and strongly encouraged to join the group.
Graduate Researchers: Send me an e-mail including your background, the project area in which you are interested, and a list of your goals for graduate school. Students interested in organic, inorganic, materials or analytical chemistry are strongly encouraged to apply to join the Smith group.
Postdoctoral applicants: Send inquiries by ‘snail mail’. Include your CV, background, what you hope to accomplish in the Smith group, and your career goals following your postdoctoral appointment. Incomplete queries or queries sent by e-mail may not be acknowledged.
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