研究领域

Organic Materials

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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Laughlin BJ, Baker WF, Duniho TL, El Homsi SJ, Tennyson AG, & Smith RC (2012) Synthesis, photophysical and electrochemical properties of conjugated polymers incorporating 9,9-dialkyl-1,4-fluorenylene units with thiophene, carbazole and triarylamine comonomers. Polymer Chemistry 3(12):3318-3323. Laughlin FL, Rheingold AL, Deligonul N, Laughlin BJ, Smith RC, Higham LJ, & Protasiewicz JD (2012) Naphthoxaphospholes as examples of fluorescent phospha-acenes. Dalton Transactions 41(39):12016-12022. He S, Buelt AA, Hanley JM, Morgan BP, Tennyson AG, & Smith RC (2012) Sterically Encumbered Bipyridyl-Derivatized Conjugated Polymers and Metallopolymers Incorporating Phenylenevinylene, Phenyleneethynylene, and Fluorenylene Segments. Macromolecules 45(16):6344-6352. Grubel K, Marts AR, Greer SM, Tierney DL, Allpress CJ, Anderson SN, Laughlin BJ, Smith RC, Arif AM, & Berreau LM (2012) Photoinitiated Dioxygenase-Type Reactivity of Open-Shell 3d Divalent Metal Flavonolato Complexes. European Journal of Inorganic Chemistry (29):4750-4757. Grubel, K.; Laughlin, B. J.; Maltais, T. R.; Smith, R. C.; Arif, A. M.; Berreau, L. M., Photochemically-induced dioxygenase-type CO-release reactivity of group 12 metal flavonolate complexes. Chemical Communications 2011, 47 (37), 10431-10433. Buelt, A. A.; Colberg, A. J.; Dennis, A. E.; Jecen, K. M.; Morgan, B. P.; Smith, R. C., Poly(p-phenylenevinylene) Derivatives with Defined Conjugation Segments and Post-Polymerization Modification with Sterically Enshrouded Chromophores. Macromolecular Rapid Communications 2010, 31 (8), 752-757. Laughlin, B. J.; Smith, R. C., Gilch and Horner-Wittig Routes to Poly(p-phenylenevinylene) Derivatives Incorporating Monoalkyl Defect-Free 9,9-Dialkyl-1,4-fluorenylene Units. Macromolecules 2010, 43 (8), 3744-3749. Mangalum, A.; Gilliard, R. J.; Hanley, J. M.; Parker, A. M.; Smith, R. C., Metal ion detection by luminescent 1,3-bis(dimethylaminomethyl) phenyl receptor-modified chromophores and cruciforms. Organic & Biomolecular Chemistry 2010, 8 (24), 5620-5627. Mangalum, A.; Morgan, B. P.; Hanley, J. M.; Jecen, K. M.; McGill, C. J.; Robertson, G. A.; Smith, R. C., Interchromophore orientation scaffolding by m-terphenyl oxacyclophanes. Chemical Communications 2010, 46 (28), 5136-5138. Mangalum, A.; Smith, R. C., Bifunctional cross-conjugated luminescent phosphines and phosphine derivatives: phospha-cruciforms. Dalton Transactions 2010, 39 (21), 5145-5151. Tennyson, E. G.; He, S.; Osti, N. C.; Perahia, D.; Smith, R. C., Luminescent phosphonium polyelectrolyte prepared from a diphosphine chromophore: synthesis, photophysics, and layer-by-layer assembly. Journal of Materials Chemistry 2010, 20 (37), 7984-7989. Coggins, M. K.; Parker, A. M.; Mangalum, A.; Galdamez, G. A.; Smith, R. C., Dizinc Phosphohydrolase Model Built on a m-Terphenyl Scaffold and Its Use in Indicator Displacement Assays for Pyrophosphate Under Physiological Conditions. European Journal of Organic Chemistry 2009, (3), 343-348 Gilliard, R. J.; Iacono, S. T.; Budy, S. M.; Moody, J. D.; Smith, D. W.; Smith, R. C., Chromophore-derivatized semifluorinated polymers for colorimetric and turn-on fluorescent anion detection. Sensors and Actuators B-Chemical 2009, 143 (1), 1-5. He, S.; Dennis, A. E.; Smith, R. C., Steric Coordination Control of Interchain Interactions in Conducting Metallopolymers. Macromolecular Rapid Communications 2009, 30 (24), 2079-2083. Mangalum, A.; Smith, R. C., Polyglycerol-bound phosphotriesterase enzyme model complexes for detection and hydrolysis of phosphorus species in aqueous solution. Tetrahedron 2009, 65 (22), 4298-4303. Morgan, B. P.; Galdamez, G. A.; Gilliard, R. J.; Smith, R. C., Canopied trans-chelating bis(N-heterocyclic carbene) ligand: synthesis, structure and catalysis. Dalton Transactions 2009, (11), 2020-2028. Morgan, B. P.; Gilliard, R. J.; Loungani, R. S.; Smith, R. C., Poly(p-phenylene ethynylene) Incorporating Sterically Enshrouding m-Terphenyl Oxacyclophane Canopies. Macromolecular Rapid Communications 2009, 30 (16), 1399-1405. Smith, R. C., Covalently Scaffolded Inter-pi-System Orientations in pi-Conjugated Polymers and Small Molecule Models. Macromolecular Rapid Communications 2009, 30 (24), 2067-2078. Tennyson, E. G.; Smith, R. C., Visible Chromophore Phosphines as Functional Elements of Luminescent Metallopolymers. Inorganic Chemistry 2009, 48 (24), 11483-11485. Coggins, M. K.; Parker, A. M.; Mangalum, A.; Galdamez, G. A.; Smith, R. C., Dizinc Phosphohydrolase Model Built on a m-Terphenyl Scaffold and Its Use in Indicator Displacement Assays for Pyrophosphate Under Physiological Conditions. European Journal of Organic Chemistry 2009, (3), 343-348. Gilliard, R. J.; Iacono, S. T.; Budy, S. M.; Moody, J. D.; Smith, D. W.; Smith, R. C., Chromophore-derivatized semifluorinated polymers for colorimetric and turn-on fluorescent anion detection. Sensors and Actuators B-Chemical 2009, 143 (1), 1-5. He, S.; Dennis, A. E.; Smith, R. C., Steric Coordination Control of Interchain Interactions in Conducting Metallopolymers. Macromolecular Rapid Communications 2009, 30 (24), 2079-2083. Mangalum, A.; Smith, R. C., Polyglycerol-bound phosphotriesterase enzyme model complexes for detection and hydrolysis of phosphorus species in aqueous solution. Tetrahedron 2009, 65 (22), 4298-4303. Morgan, B. P.; Galdamez, G. A.; Gilliard, R. J.; Smith, R. C., Canopied trans-chelating bis(N-heterocyclic carbene) ligand: synthesis, structure and catalysis. Dalton Transactions 2009, (11), 2020-2028. Morgan, B. P.; Gilliard, R. J.; Loungani, R. S.; Smith, R. C., Poly(p-phenylene ethynylene) Incorporating Sterically Enshrouding m-Terphenyl Oxacyclophane Canopies. Macromolecular Rapid Communications 2009, 30 (16), 1399-1405. Smith, R. C., Covalently Scaffolded Inter-pi-System Orientations in pi-Conjugated Polymers and Small Molecule Models. Macromolecular Rapid Communications 2009, 30 (24), 2067-2078. Tennyson, E. G.; Smith, R. C., Visible Chromophore Phosphines as Functional Elements of Luminescent Metallopolymers. Inorganic Chemistry 2009, 48 (24), 11483-11485. He, S.; Iacono, S. T.; Budy, S. M.; Dennis, A. E.; Smith, D. W.; Smith, R. C., Photoluminescence and ion sensing properties of a bipyridyl chromophore-modified semifluorinated polymer and its metallopolymer derivatives. Journal of Materials Chemistry 2008, 18 (17), 1970-1976. Iacono, S. T.; Budy, S. M.; Moody, J. D.; Smith, R. C.; Smith, D. W., Modular Approach to Chromophore Encapsulation in Fluorinated Arylene Vinylene Ether Polymers Possessing Tunable Photoluminescence. Macromolecules 2008, 41 (20), 7490-7496. Morgan, B. P.; Smith, R. C., Wide bite angle diphosphine rhodium complexes: Synthesis, structure, and catalytic 1,4-addition of arylboronic acids to enones. Journal of Organometallic Chemistry 2008, 693 (1), 11-16. 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.