春水堂视频

Research Photochemical Control of Electron-Transfer and Multielectron Chemistry using Shaped Light Fields and Molecular Structure

Research in my group involves a multifaceted approach that combines state of the art physical techniques, synthetic methodologies, and theoretical tools. The chemical questions we ask and answer lie primarily under the umbrella of physical inorganic chemistry with an emphasis on electron-transfer control, solar energy conversion, bioenergetic conversion, photocatalysis, and multielectron chemistry.

One important physical tool that is used 鈥� adaptive femtosecond pulse shaping 鈥� is a powerful recent development in laser spectroscopy. Its importance stems from the use of an adaptive learning procedure which permits the control and study of complex systems. The starting point of our adaptive control research addresses whether shaped coherent light fields can change active mechanisms of electron transfer in model and biological systems, thus, controlling electron transfer rates, direction, and multi-electron transformations.

The synthetic infrastructure built in our laboratories allows us to ask additional questions of photochemical reaction control that do not rely on the adaptive techniques. One such problem focuses on how excited-state motion in coordination complexes can be utilized to modulate 鈥� in a time-dependent fashion 鈥� the degree of coupling between an electron donor and an acceptor.

• Sartor, S. M.;听Lattke, Y. M.;听McCarthy, B. G.;听Miyake, G. M.; Damrauer, N. H.; "Effects of Naphthyl Connectivity on the Photophysics of Compact Organic Charge-Transfer Photoredox Catalysts"听Journal of Physical Chemistry A听2019,听123, 4727-4736听
• Gilligan, A. T.; Miller, E. G.; Sammakia, T.; Damrauer, N. H.; "Using Structurally Well-Defined Norbornyl-Bridged Acene Dimers to Map a Mechanistic Landscape for Correlated Triplet Formation in Singlet Fission"听Journal of the听American听Chemical听Society听2019,听141, 5961鈥�5971听
• Pearce, O.听M.; Duncan, J. S.; Damrauer,听N. H.; Dukovic, G.; "Ultrafast Hole Transfer from CdS Quantum Dots to a Water Oxidation Catalyst"听The Journal of Physical Chemistry C听2018,听122, 17559-17565听
• Sartor, S. M.; McCarthy, B. G.; Pearson, R. M.; Miyake, G. M.; Damrauer, N. H.;听"Exploiting Charge Transfer States for Maximizing Intersystem Crossing Yields in Organic Photoredox Catalysts"听Journal of the听American听Chemical听Society听2018,听140, 4778鈥�4781听
• McCarthy, B. G.; Pearson, R. M.; Lim, C.-H.; Sartor, S. M.; Damrauer, N. H.; Miyake, G. M. 鈥淪tructure-Property Relationships for Tailoring Phenoxazines as Reducing Photoredox Catalysts鈥澨�Journal of the听American听Chemical听Society听2018,听140,听5088鈥�5101.听
• Carey, T. J.; Miller, E. G.; Gilligan, A. T.; Sammakia, T.; Damrauer, N. H.听Modular Synthesis of Rigid Polyacene Dimers for Singlet Fission.听Organic Letters听2018,听20, 457-460.听
• Cook, J. D.; Carey, T. J.; Arias, D. H.; Johnson, J. C.; Damrauer, N. H.听Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer.听Journal of Physical Chemistry A听2017,听121, 9229-9242.听
• Du, Y.; Pearson, R. M.; Lim, C. H.; Sartor, S. M.; Ryan, M. D.; Yang, H.; Damrauer, N. H.; Miyake, G. M. Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals.听Chemistry - A European Journal.听2017,听23, 10962-10968.听听
• Carey, T. J.; Snyder, J. L.; Miller, E. G.; Sammakia, T.; Damrauer, N.H. Synthesis of Geometrically Well-Defined Covalent Acene Dimers for Mechanistic Exploration of Singlet Fission.听Journal of听Organic听Chemistry听2017,听82,听4866鈥�4874.听
• Fatur, S. M.; Shepard, S. G.; Higgins, R. F.; Shores, M. P.; Damrauer, N. H. A Synthetically-Tunable System to Control MLCT Excited- State Lifetimes and Spin States in Iron (II) Polypyridines.听Journal of the American Chemical Society听2017.听
• Lim, C.-H.; Ryan, M. D.; McCarthy, B. G.; Theriot, J. C.; Sartor, S. M.; Damrauer, N. H.; Musgrave, C. B.; Miyake, G. M. Intramolecular Charge Transfer and Ion Pairing in N,N-Diaryl Dihydrophenazine Photoredox Catalysts for Efficient Organocatalyzed Atom Transfer Radical Polymerization.听Journal of the听American听Chemical听Society听2016.听
• Cook, J. D., Carey, T. J. & Damrauer, N. H. Solution-Phase Singlet Fission in a Structurally Well-Defined Norbornyl-Bridged Tetracene Dimer.听Journal of听Physical听Chemistry A听2016.听
• Spettel, K. E.;听Damrauer, N. H. Exploiting Conformational Dynamics of Structurally Tuned Aryl-Substituted Terpyridyl Ruthenium(II) Complexes to Inhibit Charge Recombination in Dye-Sensitized Solar Cells.听Journal of Physical听Chemistry听C听2016, 120, 10815鈥�10829.听
• Higgins, R. F.;听Fatur, S. M.;听Shepard, S. G.;听Stevenson, S. M.;听Boston, D. J.;听Ferreira, E. M.;听Damrauer, N. H.;听Rapp茅, A. K.;听Shores, M. P.听Uncovering the Roles of Oxygen in Cr(III) Photoredox Catalysis.听Journal of the听American听Chemical听Society听2016,听138, 5451鈥�5464.听
• Shepard, S. G.;听Fatur, S. M.;听Rappe, A. K.;听Damrauer, N. H. Highly-strained iron(II) polypyridines: exploiting the quintet manifold to extend the lifetime of MLCT excited states.听Journal of the听American听Chemical听Society听2016,听138, 2949鈥�2952.听
• Arias, D. H.;听Ryerson, J. L.;听Cook, J. D.;听Damrauer, N. H.;听Johnson, J. C. Polymorphism influences singlet fission rates in tetracene thin films.听Chemical听Science.听2016,听7, 1185鈥�1191.听
• Miaja-Avila, L.; O鈥橬eil, G.C.; Joe, Y.I.; Alpert, B.K.; Damrauer, N.H.; Doriese, W.B.; Fatur, S.M.; Fowler, J.W.; Hilton, G.C.; Jimenez, R.; Reintsema, C.D.; Schmidt, D.R.; Silverman, K.L.; Swetz, D.S.; Tatsuno, H.; Ullom, J.N. Ultrafast time-resolved hard x-ray emission spectroscopy on a table top.听Physical Review X听2016,听6, 031047.听
• Damrauer, N. H.;听Snyder, J. L. Symmetry-Directed Control of Electronic Coupling for Singlet Fission in Covalent Bis-Acene Dimers.听The Journal of Physical Chemistry Letters.听2015,听6, 4456鈥�4462.听
• Alguire, E. C.; Subotnik, J. E.; Damrauer, N. H. Exploring Non-Condon Effects in a Covalent Tetracene Dimer: How Important are Vibrations in Determining the Electronic Coupling for Singlet Fission?听The Journal of Physical Chemistry A听2014,听119, 299-311.听听
• Spettel, K. E.; Damrauer, N. H. Synthesis, Electrochemical Characterization, and Photophysical Studies of Structurally Tuned Aryl-Substituted Terpyridyl Ruthenium(II) Complexes. The Journal of Physical Chemistry A. (2014) ASAP. dx.doi.org/10.1021/jp508145w
• Damrauer, R.; Lin, H.; Damrauer, N. H. Computational Studies of Carbodiimide Rings. The Journal of Organic Chemistry听 79, 3781-3788 (2014). dx.doi.org/10.1021/jo4026435
• Vallet, P. J.; Snyder, J. L.; Damrauer, N. H. Tunable Electronic Coupling and Driving Force in Structurally Well- Defined Tetracene Dimers for Molecular Singlet Fission: A Computational Exploration Using Density Functional Theory. The Journal of Physical Chemistry A.听 117, 10824鈥�10838 (2013). dx.doi.org/10.1021/jp407426q
• Hewitt, J. T.; Concepcion, J. J.; Damrauer, N. H. 听Inverse Kinetic Isotope Effect in the Excited-State Relaxation of a Ru(II)鈭扐quo Complex: Revealing the Impact of Hydrogen-Bond Dynamics on Nonradiative Decay. Journal of the American Chemical Society 135, 12500鈥�12503 (2013). dx.doi.org/10.1021/ja4037498
• Vallet, P. J.; Damrauer, N. H. Experimental and Computational Exploration of Ground and Excited State Properties of Highly Strained Ruthenium Terpyridine Complexes. The Journal of Physical Chemistry A. 117, 6489鈥�6507 (2013). dx.doi.org/10.1021/jp404248z
• Tseng, H. W. Wilker, M. B., Damrauer, N. H., Dukovic, G. Charge Transfer Dynamics between Photoexcited CdS Nanorods and Mononuclear Ru Water-Oxidation Catalysts. Journal of the American Chemical Society 135, 3383鈥�3386 (2013). dx.doi.org/10.1021/ja400178g
• McDaniel, A. M.; Tseng, H. W.; Hill, E. A.; Damrauer, N. H.; Rapp茅, A. K.; Shores, M. P. Syntheses and Photophysical Investigations of Cr(III) Hexadentate Iminopyridine Complexes and Their Tris(Bidentate) Analogues Inorganic Chemistry 52, 1368-1378 (2013). dx.doi.org/10.1021/ic302055r
• Hewitt, J. T.; Vallet, P. J.; Damrauer, N. H. Dynamics of the听3MLCT in Ru(II) terpyridyl complexes probed by ultrafast spectroscopy: evidence of excited-state equilibration and interligand electron transfer. The Journal of Physical Chemistry A 116, 11536-11547 (2012). dx.doi.org/10.1021/jp308091t
• Grumstrup, E. M.; Damrauer, N. H. Modeling and correction of distorted two-dimensional Fourier transform spectra from pixelated pulse shaping devices. Optics Express 20, 20908 (2012).听
• Vallet, P. J.; Damrauer, N. H. Computational Exploration of Heterolytic Halogen-Carbon Bond Scission Photoreactions in Ruthenium Polypyridyl Complexes (2011)听The Journal of Physical Chemistry A.听115, 3122-3132 (2011).
• Grumstrup, E. M.; Johnson, J. C.; Damrauer, N. H. Enhanced Triplet Formation in Polycrystalline Tetracene Films by Femtosecond Optical-Pulse Shaping.听Physical Review Letters听105, 257403 (2010).
• Montgomery, M. A.; Grumstrup, E. M.; Damrauer, N. H. Fourier Transform Spectroscopies Derived from Amplitude or Phase Shaping of Broad-Band Laser Pulses with Applications to Adaptive Control.听Journal of the Optical Society of America B.听27, 2518-2533 (2010).
• Meylemans, H. A.; Hewitt, J. T.; Abdelhaq, M.; Vallett, P. J.;听Damrauer, N. H. Exploiting Conformational Dynamics to Facilitate Formation and Trapping of Electron Transfer Photoproducts in Metal Complexes.听Journal of the American Chemical Society听132, 11464鈥�11466 (2010).
• McDaniel, A. M.; Tseng, H. W.; Damrauer, N. H.; Shores, M. P. Synthesis and Solution Phase Characterization of Strongly Photooxidizing Heteroleptic Cr(III) Tris-Dipyridyl Complexes: Toward Efficient Hole Transfer Sensitizers.听Inorganic Chemistry听49, 7981-7991 (2010).
• Meylemans, H. A.; Damrauer, N. H. Controlling Electron Transfer through the Manipulation of Structure and Ligand-Based Torsional Motions: A Computational Exploration of Ruthenium Donor-Acceptor Systems using Density Functional.听Inorganic Chemistry听48, 11161-11175 (2009).
• Montgomery, M. A.; Damrauer, N. H. A Convenient Method to Simulate and Visually Represent Two-Photon Power Spectra of Arbitrarily Shaped Broadband Laser Pulses.听New Journal of Physics听(Special Issue on Quantum Control Edited by H. Rabitz)听11, 105053 (2009).
• Meylemans, H. A.; Lei, C.F..; Damrauer, N. H. Ligand Structure, Conformational Dynamics, and Excited-State Electron Delocalization for Control of Photoinduced Electron Transfer Rates in Synthetic Donor鈥揃ridge鈥揂cceptor Systems听Inorganic Chemistry听47, 4060-4076 (2008).
• Grumstrup, E. M. ; Shim, S. H.; Montgomery, M. A.; Zanni, M. T.; Damrauer, N. H. Facile Collection of Two-Dimensional Electronic Spectra with Pulse Shaping Technology.听Optics Express听15, 16681-16689 (2007).
• Montgomery, M. A.; Meglen, R. R.; Damrauer, N. H. General Method for Reducing Adaptive Laser Pulse Shaping Experiments to a Single Control Variable.听J. Phys. Chem. A听111, 5126-5129 (2007).
• Montgomery, M. A.; Damrauer, N. H. Elucidation of Control Mechanisms Discovered During Adaptive Manipulation of [Ru(dpb)3](PF6)2 Emission in the Solution Phase. Journal of Physical Chemistry A.听111, 1426-1433 (2007).
• Montgomery, M. A.; Meglen, R. R.; Damrauer, N. H. Robust Basis Functions for Control from Dimension Reduction of Adaptive Pulse-Shaping Experiments.听Ultrafast Phenomena XV, R. J. D. Miller, A. M. Weiner, P. Corkum, and D. M. Jonas, eds., Springer Series in Chemical Physics, Springer, Berlin, (2006).
• Montgomery, M. A.; Meglen, R. R.; Damrauer, N.H. A General Method for the Dimension Reduction of Adaptive Control Experiments. Journal of Physical Chemistry A.听110, 6391-6394 (2006).