2014 Elected Fellow, American Academy of Arts and Sciences 2013 Inter-American Photochemical Society, Award in Photochemistry 2012 Fellow, American Chemical Society 2012 American Chemical Society Award in Inorganic Chemistry 2009 Rochester Distinguished Scholar Award 2008 National Science Foundation Award for Special Creativity 1995-1996 Japan Society for Promotion of Science Fellow 1990 Charles B. Murphy Award for Outstanding Undergraduate Teaching 1989 Frank D. Martin Undergraduate Teaching Award 1987-1991 Alfred P. Sloan Fellow 1977-1978 Elon Huntington Hooker Fellow, Rochester 1975-1979 Sherman Clarke Fellow, Rochester

Inorganic Chemistry

Our research is focused on two areas:

(1) Catalysis of the electrochemical reduction of carbon dioxide, and the photochemical "splitting" of carbon dioxide.

(2) "Ultrafast" electron transfer dynamics in inorganic mixed valence complexes.

Catalysis of the electrochemical reduction of carbon dioxide. The goal of these studies is to utilize CO2, an abundant greenhouse gas, for the ultimate manufacture of energy dense liquid fuels. These efforts have concentrated on CO2 activation and reduction of CO2 by chemical, photochemical, and electrochemical means, and the development of catalysts for transforming CO2 to organic products. Catalysts which can manage multiple proton coupled electron transfers (PCETs) to CO2 to form liquid fuels such as methanol are being developed. We are employing semiconductor devices with appropriate band energies to photochemically "split" CO2 to CO and O2.

A class of inorganic charge transfer complexes with electronic structures that can be tuned from completely delocalized to tightly localized is under investigation. At the delocaization limit, rates of intramolecular electron transfer in these systems can be so fast that coalescence of infrared spectral features occurs in a manner reminiscent of dynamic NMR, but on a picosecond (vs. millisecond for NMR) time scale. The dynamics probed by this simple IR method track solvent dipolar response, and can be developed as "reporters" of local dynamics. We expect that the fundamental knowledge gained can be applied to the rational design of "electronically wired" metal complexes and "molecular devices".

Benson EE, Sampson MD, Grice KA, Smieja JM, Froehlich JD, Friebel D, Keith JA, Carter EA, Nilsson A, Kubiak CP, "The electronic states of rhenium bipyridyl electrocatalysts for CO2 reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry.", Angew Chem Int Ed Engl, 2013, Vol. 52, Issue 18, 4841-4 [View Abstract] Kubiak CP, "Inorganic electron transfer: sharpening a fuzzy border in mixed valency and extending mixed valency across supramolecular systems.", Inorg Chem, 2013, Vol. 52, Issue 10, 5663-76 [View Abstract] Smieja JM, Sampson MD, Grice KA, Benson EE, Froehlich JD, Kubiak CP, "Manganese as a substitute for rhenium in CO2 reduction catalysts: the importance of acids.", Inorg Chem, 2013, Vol. 52, Issue 5, 2484-91 [View Abstract] Smieja JM, Benson EE, Kumar B, Grice KA, Seu CS, Miller AJ, Mayer JM, Kubiak CP, "Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO.", Proc Natl Acad Sci U S A, 2012, Vol. 109, Issue 39, 15646-50 [View Abstract] Galan BR, Schöffel J, Linehan JC, Seu C, Appel AM, Roberts JA, Helm ML, Kilgore UJ, Yang JY, DuBois DL, Kubiak CP, "Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ Complexes.", J Am Chem Soc, 2011, Vol. 133, Issue 32, 12767-79 [View Abstract] Glover SD, Kubiak CP, "Persistence of the three-state description of mixed valency at the localized-to-delocalized transition.", J Am Chem Soc, 2011, Vol. 133, Issue 22, 8721-31 [View Abstract] Goeltz JC, Kubiak CP, "Mixed valency across hydrogen bonds.", J Am Chem Soc, 2010, Vol. 132, Issue 49, 17390-2 [View Abstract] Kumar B, Smieja JM, Kubiak, CP ""Photo-reduction of CO2 on p-type silicon using Re(bipy-But)(CO)3Cl: Photovoltages exceeding 600 mV for the selective reduction of CO2 to CO."", J. Phys. Chem. C, 2010, Vol. 114, Issue 33, 14220-14223 Benson EE, Kubiak CP, Sathrum AJ, Smieja JM, "Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels.", Chem Soc Rev, 2009, Vol. 38, Issue 1, 89-99 [View Abstract]