Mikhail V. Barybin
- Chancellors Club Teaching Professor
1567 Irving Hill Road Lawrence
Lawrence, KS 66045
- Supramolecular Chemistry
Our research program is at the interface of inorganic, coordination, organic, and materials branches of chemistry. It largely involves development of organometallic and inorganic synthetic methodologies and studies of electron delocalization and transport in electron-rich organometallics. For example, we have recently devised strategies for incorporating the electronically unusual azulenic motif (a carbon framework involving fused 5- and 7-membered rings) into molecular and supramolecular hybrid metal/organic ensembles relevant for applications in molecular electronics and nanotechnology. We employ a variety of theoretical, analytical, and spectroscopic tools to assess physicochemical properties of the new compounds/materials established in our laboratory as well as guide our synthetic efforts. Among these methods are multinuclear and multidimensional NMR (including NMR of paramagnetic molecules and ions), organic and organometallic electrochemistry, single crystal X-ray crystallography, electronic and vibrational spectroscopies, Density Functional Theory calculations, and various surface and imaging techniques. The current projects can be grouped into the following categories:
- Azulene-based organometallics: toward new hybrid metal/organic compounds and materials with unusual electron transport and optical properties
- Reversible electron-rich electrochromic systems, compact molecular electron reservoirs
- Designed organic surfaces for electronics or sensing applications
Selected Publications —
Connelly, P.T., Applegate, J.C., Maldonado, D.A., Okeowo, M.K., Henke, W.C., Oliver, A.G., Berrie, C.L., and Barybin, M.V. Homoleptic complexes of isocyano-and diisocyanobiazulenes with a 12-electron, ligand-based redox capacity. Dalton Trans., 2023, 52, 11419-11426. https://doi.org/10.1039/D3DT01958F
Hart, M.D.; Meyers, J.J., Jr.; Wood, Z.A.; Nakakita, T.; Applegate, J.C.; Erickson, N.R.; Gerasimchuk, N.N.; Barybin, M.V. Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered. Molecules 2021, 26, 981.
Fathi-Rasekh, M.; Rohde, G. T.; Hart, M. D.; Nakakita, T.; Zatsikha, Y. V.; Valiev, R. R.; Barybin, M. V.; Nemykin, V. N. “Positional Isomers of Isocyanoazulenes as Axial Ligands Coordinated to Ruthenium(II) Tetraphenylporphyrin: Fine-Tuning Redox and Optical Profiles,” Inorganic Chemistry 2019, 58, 9316-9325.
Wächter, T.; Scheetz, K. J.; Spaeth, A. D.; Barybin, M. V.; Zharnikov, M. “Dynamics of Electron Transfer in Azulene-Based Self-Assembled Monolayers,” Journal of Physical Chemistry 2017, 121, 13777-13785.
Applegate, J. C.; Okeowo, M. K.; Erickson, N. R.; Neal, B. M.; Berrie, C. L.; Gerasimchuk, N. N.; Barybin, M. V. “First p-linker featuring mercapto and isocyano anchoring groups within the same molecule: Synthesis, heterobimetallic complexation and selfassembly on Au(111),” Chemical Science 2016, 7, 1422-1429.
Nemykin, V. N.; Dudkin, S. V.; Fathi-Rasekh, M.; Spaeth, A. D.; Rhoda, H. M.; Belosludov, R. V.; Barybin, M. V. “Probing Electronic Communications in Heteronuclear Fe-Ru-Fe Molecular Wires Formed by Ruthenium(II) Tetraphenylporphyrin and Isocyanoferrocene or 1,1′-Diisocyanoferrocene Ligands,” Inorganic Chemistry 2015, 54, 10711-10724.
Nakakita, T.; Miura, M.; Toriyama, M.; Motohashi, S.; Barybin, M. V. “Remote induction of stereoselective 1,2-addition of aryl Grignard reagents to b-sulfinyl enones,” Tetrahedron Letters 2014, 55, 1090-1092.
Nemykin, V. N.; Purchel, A. A.; Spaeth, A. D.; Barybin, M. V. "Probing Electronic Properties of a Trinuclear Molecular Wire Involving Isocyanoferrocene and Fe(II) Phthalocyanine Motifs," Inorg. Chem. 2013, 52, 11004-11012. (Cover Article)
Scheetz, K. J.; Spaeth, A. D.; Vorushilov, A. S.; Powell, D. R.; Day, V. W.; Barybin, M. V. "The 2,6-Dimercaptoazulene Motif: Efficient Synthesis and Completely Regioselective Metallation of its 6-Mercapto Terminus," Chem. Sci. 2013, 4, 4267-4272.
Maher, T. R.; Meyers, J. J., Jr.; Spaeth, A. D.; Lemley, K. R.; Barybin, M. V. "Diisocyanoarene-linked Pentacarbonylvanadate(I-) Ions as Building Blocks in a Supramolecular Charge-Transfer Framework Assembled through Noncovalent π-π and Contact Ion Interactions,” Dalton Trans. 2012, 41, 7845-7848 (invited contribution to the special issue New Talent: the Americas).
Barybin, M. V.; Meyers, J. J., Jr.; Neal, B. M. Renaissance of Isocyanoarenes as Ligands in Low-Valent Organometallic Chemistry. In Isocyanide Chemistry: Applications in Synthesis and Material Science. Nenajdenko, V., Ed. Wiley-VCH: Weinheim, 2012, pp 493-529. (ISBN-10: 3-527-33043-7)
Neal, B. M.; Vorushilov, A. S.; DeLaRosa, A. M.; Robinson, R. E.; Berrie, C. L.; Barybin, M. V. "Ancillary Nitrile Substituents as Convenient IR Spectroscopic Reporters for Self-Assembly of Mercapto- and Isocyanoazulenes on Au(111)," Chem. Commun. 2011, 47, 10803-10805.
McGinnis, D. M.; Deplazes, S. F.; Barybin, M. V. “Synthesis, properties and complexation of (pS)-1-isocyano-2-methylferrocene, the first planar-chiral isocyanide ligand,” J. Organomet. Chem. 2011, 696, 3939-3944 (Special Issue on Small Molecule Activation and Catalysis Invoking Metal-Carbon Multiple Bonds).