Dr. Kim R. Dunbar Distinguished Professor
Inorganic Chemistry Research in the Dunbar group spans topics in synthetic, structural and physical inorganic and bioinorganic chemistry. The use of a range of tools including spectroscopy, X-ray crystallography, magnetometry, electron microscopy, mass spectrometry and electrochemistry reflect the breadth of problems under investigation.
Ph.D., Purdue University Phone: (979) 845-5235 Fax: (979) 845-7177 dunbar@mail.chem.tamu.edu Selected Publications Pentanuclear Trigonal-Bipyramidal Cyanide Complexes: A Powerful Platform for the Systematic Assessment of the Magnetic Properties of Cyanide-Bridged Compounds. Funck, K. E.; Hilfiger, M. G.; Berlinguette, C. P.; Shatruk, M.; Dunbar, K. R. Forum issue on Molecular Magnetism, Inorg. Chem., 2009, 48, 3438-3452. Cyanide-Bridged Complexes of Transition Metals: A Molecular Magnetism Perspective. Shatruk, M.; Avendaño, C.; Dunbar, K. R. Prog. Inorg. Chem., 2009, 56, 155-334. Schottel, B. L.; Chifotides, H. T.; Dunbar, K. R. Anion-π Interactions: A Tutorial Review. Chem. Soc. Rev. 2008, 37, 68–83 Hexacyanoosmate(III) chemistry: Preparation and magnetic properties of a pentanuclear cluster and a Prussian blue analogue with Ni(II). Hilfiger, M.; Shatruk, M.; Prosvirin, A.; Dunbar, K. R.Chem. Commun., 2008, 5752 – 5754. Nazario, L.; Zhao, H.; Prosvirin, A. V.; Chouai, A.; Shatruk, M.; Dunbar, K. R. Conversion of a Porous Material Based on a Mn(II)-TCNQF4 Honeycomb Net to a Molecular Magnet Upon Desolvation. Chem. Commun. 2007, 44, 4611-4613.
Molecular Magnets, Conducting Metal-Organic Solids and SpinCrossover Compounds. The study of molecule-based, metal containing materials with conducting, optical, and/or magnetic properties is an area that presents considerable synthetic challenges. Of particular interest are "hybrid" solids that combine two or more properties not traditionally found in the same material. One of our approaches is to combine paramagnetic metal centers and conducting organic sub-lattices. In this vein, we are designing molecules as well as, 1-D, 2-D and 3-D materials with transition or lanthanide metal ions connected by organic radicals. Materials that exhibit high conductivity, magnetic ordering as well as “single molecule magnetism” have been discovered. In another project we are exploring cyanide chemistry of 3d, 4d and 5d transition metals by a step-wise building block approach to prepare families of molecules with predictable geometries whose magnetic properties are modulated by deliberate changes in the molecule. We have synthesized magnetic molecular squares, cubes, trigonal bipyramids and other architectures that display single-molecule magnetism, charge-transfer induced spin transitions, spin-crossover at high temperatures, and photoinduced magnetic behavior. A remarkable finding is that heterobimetallic clusters as small as five metal atoms mimic the properties previously observed only for 3-D “Prussian-Blue” type magnetic materials. Metals in Medicine. We have developed a program to address several issues in the area of metals in medicinal applications. The main synthetic targets are dirhodium compounds that are known to exhibit carcinostatic activity and ruthenium agents. Among our goals are to (1) to elucidate sites of binding to biological molecules including DNA and characterize adducts by NMR and X-ray techniques, (2) to develop redox-active compounds that exhibit low cytotoxity in the dark but which cleave DNA and cause cellular death under irradiation and (3) to design new generations of compounds with ligands that stabilize the dinuclear core and cause a red-shift in the electronic transition that is responsible for the photocytotoxity. The ultimate goal of the research is to develop photodynamic therapy drugs.
Anion-pi Interactions. Anion-pi interactions are gaining significant recognition but their pivotal role in chemical and biological processes is only beginning to be appreciated. Research in this nascent area of supramolecular chemistry began in our group with the synthesis and X-ray structures of cationic metal assemblies with encapsulated anions. Chifotides, H. T.; Dunbar, K. R. Interactions of Computational studies have confirmed the presence of anion-heterocyclic Metal—Metal-Bonded Antitumor Active ring contacts for electropositive ring systems and new experimental work Complexes with DNA Fragments and DNA. Acc. has led to a deeper understanding of the guiding principles of this exciting Chem. Res. 2005, 38, 146-156. The Association of Former Students Distinguished Award for Graduate Mentoring, Purdue University Department new Achievement area. Intercalation Is Not Required for DNA LightSwitch Behavior. Lutterman, D. A.; Chouai, A.; Liu, Y.; Sun, Y.; Stewart, C. D.; Dunbar, K. R.; Turro, C. J. Am. Chem. Soc., 2008; 130, 11631170.
of Chemistry Distinguished Alumna Award, Elected Fellow of American Association for the Advancement of Science, NSF Creativity Grant Extension Award, Distinguished Alumna Award, Westminster College