Research Interests

Our main research interests are in the field of bio-inorganic, materials, and computational chemistry. More specifically, we are interesting in: i) modeling of oxygen-atom transfer reactivity and electron pathway in the mononuclear tungstopterin enzymes; ii) compounds for molecular electronics and mixed-valence complexes; iii) prediction of the electronic structure, stability, and spectroscopic properties of transition-metal complexes. Recently, we have reported the several new molybdenum complexes, which exhibit discrete oxygen atom transfer reactivity and were able to isolate key reaction intermediates. Our current bio-inorganic projects are dealing with the different “scorpionate” and dithiolate tungsten complexes as well as with iron-sulfur clusters.

Another area of our research interests includes synthesis, characterization, and theoretical modeling of polyferrocenyl-containing porphyrins, tetraazaporphyrins, and phthalocyanine macrocycles. In this project, we are trying to understand the influence of the different factors on the long-range metal-metal coupling.

Finally, we are interesting in development of computational approaches and use of modern density functional theory methods for the calculation and accurate prediction of the absorption, NMR, IR, EPR, and Mössbauer spectral parameters in the transition-metal complexes (VMOdes page is here and some useful tips on Gaussian program are here).

Representative Publications (full list of publications available here)

Nemykin, V. N.; Laskin, J.; Basu, P. “Isolation, Characterization of an Intermediate in an Oxygen Atom-Transfer Reaction, and the Determination of the Bond Dissociation Energy,” J. Am. Chem. Soc. , 126 , 8604-8605 (2004).

Nemykin, V. N.; Basu, P. “A bifurcated pathway of oxygen atom transfer reactions from a monooxo molybdenum(VI) complex under electrospray ionization mass spectrometric conditions,” Dalton Transactions , 1928-1933 (2004).

Basu, P.; Nemykin, V. N.; Sengar, R. “Synthesis, spectroscopy, and redox chemistry of encapsulated oxo-Mo(V) centers: implications for pyranopterin-containing molybdoenzymes,” Inorg. Chem. , 42 , 7489-7501 (2003).

Nemykin, V. N.; Basu, P. “A Comparative Theoretical Investigation of the Vertical Excitation Energies and the Electronic Structure of [Mo^VOCl₄]^- : Influence of Basis Set and Geometry,” Inorg. Chem. , 42 , 4046-4056 (2003) .

Nemykin, V. N.; Davie, S. R.; Mondal, S.; Rubie, N.; Kirk, M. L.; Somogyi, A.; Basu, P. “An Analogue System Displaying All the Important Processes of the Catalytic Cycles Involving Monooxomolybdenum(VI) and Desoxomolybdenum(IV) Centers,” J. Am. Chem. Soc. , 124 , 756-757 (2002).

Kobayashi, N.; Miwa, H.; Nemykin, V. N. “Adjacent versus Opposite Type Di-Aromatic Ring-Fused Phthalocyanine Derivatives: Synthesis, Spectroscopy, Electrochemistry, and Molecular Orbital Calculations,” J. Am. Chem. Soc. , 124 , 8007-8020 (2002).

Kobayashi, N.; Inagaki, S.; Nemykin, V. N.; Nonomura, T. “A novel hemiporphyrazine comprising three isoindolediimine and three thiadiazole units,” Angew. Chem., Int. Ed. , 40 , 2710-2712 (2001).

Nemykin, V. N.; Kobayashi, N.; Chernii, V. Y.; Belsky, V. K. “Mössbauer, crystallographic, and density functional theoretical investigation of the electronic structure of bis-ligated low-spin iron (II) phthalocyanines,” Eur. J. Inorg. Chem. , 733-743 (2001).

Some available equipment in the lab, department, or as a part of collaboration (if you would like to see the list of equipment with pictures, which is a large file, click here):

A new Varian 500 MHz as well as two 300 MHz spectrometers are available for research including high-sensitivity and low-frequency probes.

Single crystal X-ray diffraction experiments are performed on our Rigaku AFC7R rotating anode X-ray diffractometer that is equipped a Mo Ka radiation. Cu and Ag anodes are also available. In addition, small crystals and specific experiments can be done at Victor Young's lab at University of Minnesota Twin Cities campus.

Our Brucker EPR spectrometer is rather old, but was recently updated with new computer interface and other features.

Several Hewlett-Packard IR spectrometers can be routinely used to study vibration spectra of new compounds.

We have several UV-Vis-NIR spectrometers from Hewlett-Packard and Ocean Optics, which allow us to study optical properties of new complexes.

Our Cary fluorimeter from Varian is used to study the excited states properties of our new materials.

ESI/APCI LC and MALDI-TOF mass spectrometers are available at the Twin Cities campus and hopefully will be available too at UMD soon.

Electrochemical and spectroelectrochemical equipment is available for the investigation of redox properties of new compounds.

A new MBraun LabMaster glove box with a single filter column gas purification system is used for the manipulation of air-sensitive and moisture-sensitive products and starting materials.

Some of our reactions are carried out under inert atmosphere and several inert gas/vacuum lines are available in the lab.

A new solvent purification system does not require any distillation.

Several powerful PC-based workstations (i.e. P4, 3.6 GHz, 2 Gb of 533 MHz RAM, 2 10,000 prm HDD in Raid 0 configuration) along with possibility to work on Minnesota Supercomputing Institute facilities are available for the DFT calculations.

Our research has benefited from excellent collaborative support from:

Prof. Viktor Zhdankin, UMD

Prof. Paul Kiprof, UMD

Prof. Robert Carlson, UMD

Prof. James Riehl, UMD

Prof. Partha Basu, Duquesne University

Prof. Alex Nazarenko, Buffalo State College

Prof. Nick Gerasimchuk, Southern Missouri State University

Dr. Douglas Fox, Gaussian Inc.

Prof. Keichii Sakamoto, Nihon University, Japan

Prof. Rodion Belosludov, Tohoku University, Japan

Prof. Eugenii A. Lukyanets, NIOPIK, Russia

Dr. Vladimir Mytsik, IGIC, Ukraine

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