Research Interests

Our interests focus on coordination chemistry and understanding the synergistic relationships between metals and ligands in biomolecules and materials. While the coordination of small molecules to metal centers is relatively well understood, the effect of complex ligand environments is still an area of intense investigation. Our research examines metal ions in complex coordination environments, such as macrocycles, proteins and advanced materials.

Metalloporphyrins and phthalocyanines have been studied for more than a century and many researchers have probed the relationship between macrocycle structure and the metal center. However, the metal complexes of porphyrin isomers (such as porphycene or N-confused porphyrin), porphyrin analogs (such as corrole and isocorrole) and other pyrrolic macrocycles have not been as extensively studied. Not only are porphyrin isomers and analogs excellent potential ligands for transition metals, but these compounds also can be used to examine the effects of aromaticity and central pore size on metal structure and reactivity.  We have also explored a family of phthalocyanine analogs known as the hemiporphyrazines.  As in N-confused porphyrin, the hemiporphyrazines can bind metal ions in unusual geometries.  We can also use synthetic methodologies with the reagent diiminoisoindoline to fabricate new and unusual phthalocyanine variants.  Our work has recently extended to pyrrole-based fluorescent materials, including azaBODIPYs as well as our recently discovered BOPHY fluorophore.

We have also begun to explore the chemistry of organometallic complexes in aqueous systems.  Normally, organometallic bonds are highly sensitive to both dioxygen and water.  However, certain metal ions, especially those with d6 electron counts, can form complexes that are stable in aerobic aqueous conditions.  We are currently exploring the chemistry of compounds containing the Re(CO)3+ moiety and have extended our investigations into ferrocenes and other metallocenes with reactive functional groups that will enable covalent conjugation to biological macromolecules.

Selected Publications

  1. Tamgho, I.-S.; Hasheminasab, A.; Engle, J. T.; Nemykin, V.N.; Ziegler, C.J. “A new highly fluorescent and symmetric pyrrole-BF2 chromophore: BOPHY” Journal of the American Chemical Society, 2014, 136(15) 5623-5626.

  2. Wang, L.; Tamgho, I. -S.; Crandall, L. A.; Rack, J.J.; Ziegler, C.J. “Ultrafast dynamics of a new class of highly fluorescent boron difluoride dyes” Physical Chemistry Chemical Physics, 2015, 17(4), 2349-2351.

  3. Rhoda, H.; Crandall, L. A; Geier, G. R .; Ziegler, C.J.; Nemykin, V.N. “Combined MCD/DFT/TDDFT study of the electronic structure of axially coordinated metallocorroles” Inorganic Chemistry, (2015), 54(10), 4652-4662.

  4. Hasheminasab, A.;  Wang, L.; Dawadi, M. B.; Bass, J.;  Herrick, R. S.; Rack, J. J.; Ziegler, C. J. “Induction of E/Z isomerization in a pendant metal-bound azobenzene: A synthetic, spectroscopic and theoretical study”  Dalton Transactions, 2015, 44(35), 15400-15403.

  5. Hasheminasab, A.; Rhoda, H. M.; Crandall, L. A.; Ayers, J. T.; Nemykin, V. N.; Herrick, R. S.; Ziegler, C. J.  “Hydrazine-mediated strongly coupled Re(CO)3 dimers” Dalton Transactions, 2015, 44, 17268 -17277.

  6. Rhoda, H. M.; Chanawanno, K.; King,  A.J.; Zatsikha, Y.V.; Ziegler, C.J.; Nemykin, V.N. "Unusually strong long-distance metal-metal coupling in bis(ferrocene)-containing BOPHY: Introduction to organometallic BOPHYs"  Chemistry - A European Journal (2015), 21(50), 18043-18046.

  7. Chanawanno, K.; Kondeti, V.; Caporoso, J.; Paruchuri, S.; Leeper, T. C.; Herrick, R. S.; Ziegler, C.J. “Facile rhenium-peptide conjugate synthesis using a one-pot derived Re(CO)3 reagent” Dalton Transactions (2016), 45(11), 4729-4735.

  8. Crandall, L.A.; Bogdanowicz, C. A.; Hasheminasab, A.; Chanawanno, K.; Herrick, R. S.; Ziegler, C.J. “Re(CO)3-templated formation of aza(dibenzo)dipyrromethenes”  Inorganic Chemistry (2016), 55(7), 3209-3211.

  9. Hasheminasab, A.; Dawadi, M. B.; Mehr, H. S.; Herrick, R. S.; Ziegler, C.J.   “Re(CO)3  metallopolymers with complete metal monomer incorporation: synthetic, spectroscopic, electrochemical, and computational studies” Macromolecules (2016), 49(8), 3016-3027.

  10. Osinski, A.J.; Blesener, T.S.; Hasheminasab, A.; Holstrom, C.; Nemykin, V.N.; Ziegler, C.J.  “Re(CO)3-Templated Synthesis of Semihemiporphyrazines”  Inorganic Chemistry 2017 55 (24), 12527-12530

  11. Morris, D.L.; Zampino, A.P.; Taraboletti, A.A.; Shriver, L.P.; Leeper, T.C.; Ziegler C.J. “Lysozyme-catalyzed formation of a conjugated polyacetylene”  Polymer Chemistry 2017 8 (41), 6344-6348

  12. Schrage, B.R.; Zhao, Z.; Ziegler, C.J.; Boika A. “Cation‐Anion Redox Switching in an All‐Ferrocene Salt”  ChemElectroChem  2018 5 (23), 3624-3627

  13. Zatsikha, Y.V.; Blesener, T.S.; Goff, P.C.; Healy, A.T.; Swedin, R.K.; Herbert, D.E.; Rohde, G.T.; Chanawanno, K.; Ziegler, C.J.; Belosludov, R.V.; Blank, D.A.; Nemykin V.N. “1, 7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?”  The Journal of Physical Chemistry C  2018 122 (49), 27893-27916