1. Magnetostructural correlations in itinerant magnets. Itinerant magnets represent a peculiar class of materials, whose magnetic behavior is strongly dependent on the nature of electronic structure in the vicinity of the Fermi level, and therefore can be effectively tuned by controlling the band structure of the solid. While such materials traditionally have been a focus of condensed matter physics, the fast-paced development of methods for electronic structure calculations and appearance of reliable user-friendly codes allow solid state chemists to become actively involved in this area of research. This trend has been reinforced by the recent discovery of FeAs-based superconductors, which caused a renewed interest to the ThCr2Si2 structure type in the solid-state chemistry community. Our research thus far has focused on elucidating correlations between the crystal and electronic structures and magnetic properties of RCo2Pn2 materials (R = rare earth; Pn = P, As) to achieve better understanding and control over the type and temperature of magnetic ordering in these systems. We are also interested in exploring R-rich sections of the R-T-X phase diagrams (T = transition metal; X = Si, Ge, Sn) for the discovery of new 3d-4f coupled itinerant magnets. Summarized below are the most important achievements on this project (funded by the NSF CAREER award): (1) control of ferromagnetic ordering temperature in La1–xPrxCo2P2 via modification of interlayer Co-Co interactions; (2) stabilization of a homogeneous mixed-valence state of Eu by means of chemical compression that results in the change from antiferromagnetism in PrCo2P2 and EuCo2P2 to ferromagnetism in Pr0.8Eu0.2Co2P2; (3) generation of a spin-glass state in LaFexCo2–xP2, with a possible formation of a rare Griffiths-like state; (4) synthesis of ternary RCo2As2 from Bi flux and the first report of their magnetic properties; (5) a detailed structural analysis of a giant unit cell compound Sm117Co56Sn112 and its rare-earth analogs, and elucidation of their magnetic behavior.
2. Multifunctional spin-crossover materials. Certain complexes of d4-d7 transition metals exhibit magnetic bistability, a transition between the low-spin and high-spin states commonly referred to as spin crossover (SCO). They represent great interest with regard to the development of new paradigms in molecular electronics and high-density data storage. Our group is exploring hybrid materials that combine such complexes with (a) conducting charge-transfer salts, (b) luminescent quantum dots, or (c) divergent linkers that can lead to the formation of multinuclear spin-crossover complexes or coordination polymers. To achieve these goals, we use a combination of synthesis, crystal structure analysis, and magnetic measurements, as well as various spectroscopic techniques to create novel materials with magnetically bistable Fe(II) centers. On this NSF-funded project, the most important achievements are: (1) functionalization of well-known Fe(II) SCO complexes with tetrathiafulvalene (TTF), a ubiquitous component of synthetic organic conductors. We now work on obtaining conducting SCO materials via electrooxidation of the obtained TTF-containing Fe(II) complexes; (2) preparation of several multinuclear clusters, in which Fe(II) SCO centers are bridged by cyanide or dicyanometallate linkers; (3) discovery of a robust ligand set that contains 2,2′-biimidazole and preserves SCO at the Fe(II) center upon alkylation of the ligand: this allows functionalization of the SCO complexes, facilitating their assembly on various substrates, such as thin films, nanotubes, or nanoparticles; (4) preparation of a complex with an alkylated derivative of biimidazole; the complex exhibits an abrupt SCO with thermal hysteresis and a photoinduced transition between the spin states at low temperature.
3. Panchromatic solar-cell sensitizers. The last two decades have witnessed an exponential growth of research on dye-sensitized solar cells (DSSCs) – an appealing alternative energy technology. Since light-harvesting is the key process in the DSSC device, many efforts have been devoted to increasing the absorptivity and stability of the dyes. Among these, Ru polypyridine complexes exhibit remarkable performance owing to their strong absorption in the visible range and long-lived charge-separated excited states. Nevertheless, the insufficient coverage of the visible range and the lability of thiocyanate ligands that are widely used in “champion” dyes are among the problems that impede further increases in the power-conversion efficiency. Dipyrrins, commonly used as precursors to porphyrin macrocycles, are strongly absorbing molecules that act as stable chelating ligands towards metal ions. Our group was among the first to report panchromatic Ru-dipyrrin complexes that possess appropriate photophysical and electrochemical characteristics to be used as solar-sell sensitizers. Current research focuses on testing these dyes in DSSC devices and continuing development of more efficient sensitizers guided by the results of DSSC tests and theoretical calculations at the DFT level.
Wang, J.; Ozarowski, A.; Kovnir, K.; Thompson, C. M.; Yaroslavtsev, A. A.; Chernikov, R. V.; Dalal, N.; Shatruk, M. Trimetallic [M3(dpa)4]2+ complexes (M = Co, Ni) as building blocks for cyanide-bridged coordination polymers. Eur. J. Inorg. Chem.2012, DOI: 10.1002/ejic.20
Li, G.; Bomben, P. G.; Robson, K. C. D.; Gorelsky, S. I.; Berlinguette, C. P. Shatruk, M. Ru complexes of thienyl-functionalized dipyrrins as NCS-free sensitizers for the dye-sensitized solar cell. Chem. Commun.2012, 47, DOI: 10.1039/c2cc343
Li, G.; Ray, L.; Glass, E. N.; Kovnir, K.; Khoroshutin, A.; Gorelsky, S. I.; Shatruk, M. Synthesis of panchromatic Ru(II) thienyl-dipyrrin complexes and evaluation of their light-harvesting capacity. Inorg. Chem.2012, 51, 1614-1624.
Kovnir, K.; Garlea, V. O.; Thompson, C. M.; Zhou, H. D.; Reiff, W. M.; Ozarowski, A.; Shatruk, M. Spin-glass behavior in LaFexCo2-xP2 solid solutions: Interplay between magnetic properties and crystal and electronic structures. Inorg. Chem.2011, 50, 10274-10283.
Kovnir, K.; Shatruk, M. Magnetism in giant unit cells: Crystal structure and magnetic properties of
R117Co52+δSn112+γ (R = Sm, Tb, Dy). Eur. J. Inorg. Chem.2011, 3955-3962.