Silas Blackstock

Silas C. Blackstock

Professor

Education

  • Postdoctoral Associate, Yale University, 1986-1988
  • Postdoctoral Associate, University of Houston, 1985-1986
  • PhD, University of Wisconsin, 1985
  • BS, Baylor University, 1979

Research Areas

  • Electron transfer chemistry and catalysis
  • High-spin polyradical ions, molecular charge storage, redox-gradient dendrimers
  • Electron donor-acceptor bonding
  • Nitrosobenzenes and dynamic covalent bonding
  • Organic assemblies in water

Research

Organic electron transfer (ET) chemistry is a major area of our research. We study how electron loss affects molecular structure, properties, and reactivity. From a physical organic analysis of radical cation structure and reactivity, we develop new ET-mediated transformations and ET materials.

By linking redox-active (redox auxiliary, RA) groups to thermally reactive functions, we are developing a generalized approach to ET-catalysis, which we call ‘redox-auxiliary catalysis’ (patent 2016), which has been applied to photoactive norbornadienes and azobenzenes to make new photo-electro-switchable materials, with applications in solar energy storage and nanomechanical operations.

A long-standing interest of ours is e-donor/e-acceptor bonding between e-rich and e-poor organic functions. Such supramolecular attractions can be used to guide crystal and cocrystal formations, as a new tool for crystal engineering.

Most recently, we are exploring the unique dynamic covalent bonding of nitrosobenzenes, which offers a new means of molecular docking and reconnections in ‘smart’ chemical systems. As part of these studies, we investigate the covalent and noncovalent assembly of these and other molecules in water, which offers a special venue for organic molecular associations and formation of new ‘states’ of organic structures with new chemical properties.

Our research involves organic synthesis, electrochemistry, NMR and ESR spectroscopy, photochemistry, x-ray crystallography, optical spectroscopy and probe microscopy.

Selected Publications

Controlling Chemical Dynamics of Molecular Assemblies through Nanoconfinement: o-Nitrosocumene@Pd Nanocage” Pradeep, A.; Rogers, C. R.; Marek, R.; Blackstock, S. C.; Ramamurthy, V. J. Org. Chem. 202691, 9679-9690.  http://doi.org/10.1021/acs.joc.6c00239

Supramolecular Confinement as a Tool to Control the Dynamic Molecular Assembly of o-Nitrosocumene in Water” Pradeep, A.; Rogers, C. H.; Varadharajan, R.; Kelley, S. A.; Marek, R.; Blackstock, S. C.; Ramamurthy, V. Chem. Commun. 2025, 61, 19265-19268. DOI: 10.1039/d5cc04999g

Dynamic covalent and noncovalent assembly of o-nitrosocumene in organic solvents and water”  Rogers, C. H.; Pradeep, A.; Galiano, L. A.; Kelley, S. A.; Varadharajan, R; Belmore, K.; Whitt, L. M.; Li, Y.; Champagne, P. A.; Ramamurthy, V.; Blackstock, S. C. Chem. Commun.202460, 13899-13902.

Organic Host Encapsulation Effects on Nitrosobenzene Monomer-Dimer Distribution and C-NO Bond Rotation in an Aqueous Solution,” Varadharajan, R.; Kelley, S. A.; Jayasinghe-Arachchige, V. M.; Prabhakar, R.; Ramamurthy, V.; Blackstock, S. C. ACS Org. Inorg. Au, 2022, 2, 175–185.  Journal cover

Photo-Electro-Switchable Arylamino-Aobenzenes,” Saint-Louis, C. J.; Warner, D. J.; Keane, K. S.; Kelley, M. D.; Meyers, C.; Blackstock, S. C., J. Org. Chem. 2021,86, 11341-11353

Bridged Azobenzenes and Their Chemical Applications.” Warner, D. J., Keane, K. S. and Blackstock, S. C.  In The Chemistry of Nitrogen-Rich Functional Groups; Liebman, J. F., Greer, A., Eds.; Patai’s Chemistry of Functional Groups Series, John Wiley & Sons, 2019, ch 4; pp 65-113.

Bridged Azobenzenes and Their Biological Applications,” Warner, D. J., Keane, K. S., Saint‐Louis, C. J. and Blackstock, S. C.  In The Chemistry of Nitrogen-Rich Functional Groups; Liebman, J. F., Greer, A., Eds.; Patai’s Chemistry of Functional Groups Series, John Wiley & Sons, 2019, ch 9; pp 251-285

Evaluating the Large Magnetic Anisotropy of the Nitroso Group in Oriented Nitrosoarenes,” Owens, C. E.; Kelley, S. A.; Blackstock, S. C. JOSHUA (The Journal of Science and Health at the University of Alabama), 2018,15, 26-31

Redox Auxiliary Catalysis,” Blackstock, S. C.; Gray, L. T., III; Kelley, M. D.; Saint-Louis, C. J. U.S. Patent 9,469,602 B2, Oct 18, 2016