С��Ƭ��Ƶ

Our research group is primarily interested in organometallic and coordination chemistry.  One particular area of interest involves the design, isolation and stabilization of metal complexes which aid in exploring the commonly accepted ideas of bonding.  For example, we are interested in the synthesis of low-coordinate main group, d-block, and f-block complexes with unusual bonding modes and oxidation states. This work is focused on the development of new synthetic methodologies and the use of sterically demanding ligand systems to support novel unsaturated and highly reactive compounds.  From a fundamental structure/bonding viewpoint, the isolation of such complexes is essential if a comprehensive understanding is to be attained. Additionally, from a more applied perspective, we are also interested in the examination of the structure/activity relationships of low-coordinate and highly reactive metal centers with a goal of their exploitation in catalysis.  The group utilizes standard Schlenk line and glove box techniques for the manipulation of air-sensitive compounds. The characterization of new complexes typically includes single crystal X-ray diffraction, multinuclear NMR, FT-IR and UV/VIS spectroscopy. 

These investigations, while rooted in traditional aspects of chemistry, will often involve students in collaborations with an array of other scientists and engineers. Group members will have their own projects; however, each group member's research will have significant overlap with others in the group. As such, the students' depth of fundamental chemical principles will become augmented by exposure to a breadth of additional concepts. It is anticipated that such a combination of skills results in a fertile and created environment for achievement of research goals. Therefore, students should frequently expand beyond the reaches of classical chemistry subjects, and embrace additional areas, as required, for the successful execution of a specific project.

One component of our research is further elaborated on in the following paragraph. For more information see the selected publications below.

The Design of Metal-Organic Complexes Utilizing a Synergistic Approach

In a number of metalloproteins hydrogen bonding (5 to 15 kcal/mol) is used in conjunction with metal-ligand covalent bonds to control activity within biomolecules. A current research challenge in synthetic inorganic chemistry is the incorporation of these types of interactions into well-defined metal compounds with the intention of developing enhanced catalytic and stoichiometric reactivity. Conversely, difficulties arise in synthetic systems because their structures are often flexible, so H-bonds form with various other species present, such as solvent molecules or counterions. These intermolecular hydrogen bonds are often unwanted and interfere with the desired function. Therefore, as in metalloproteins, synthetic complexes must have a combination of ligands placed within rigid frameworks located near the metal center(s) to ensure stable complex formation. Our research group utilizes a combination of novel set of ligands in conjunction with a vast array of metals throughout the Periodic Table to produce well designed multi-functional inorganic/organic hybrid systems. Students working in this area frequently expand beyond the reaches of classical chemistry subjects and embrace additional areas, as required, for the successful execution of a specific project. Standard Schlenk and glovebox techniques are employed to synthesize a variety of low-coordinate air and moisture sensitive inorganic complexes.

Scholarly, Creative & Professional Activities

(2012 to present)

(* denotes corresponding author, italics denotes undergraduate student)

1. Tandon*, S. S., Bunge, S. D., Patel, N., Sanchiz, J. “H-bonding directed formation of 1D-single chains, 2D-sheets, and 3D structures in magnetically coupled tetranuclear nickel(II) complexes with incomplete double cubane core”. Polyhedron, 2017 123, 361-375.  
2. Al-Shadeedi, A., Liu, S., Keum, C. M., Kasemann, D., Hossbach, C., Bartha, J., Bunge, S. D., Lussem*, B. “Minority Currents in n-Doped Organic Transistors” ACS Appl. Mater. Interfaces, 2016 8, 32432-32439.  
3. Keum, C. M., Liu, S. Y., Al-Shadeedi, A., Kaphle, V., Bunge, S. D., Lussem*, B. “Charge trapping in doped organic Zener diodes” Organic Electronics, 2016 39, 77-84.  
4. Khattab*, T. A., Tiu, B. D. B.,  Adas, S., Bunge, S. D., Advincula,  R. C. “pH triggered smart organogel from DCDHF-Hydrazone molecular switch” Dyes and Pigments 2016 130, 327-336.  
5. Khattab*, T. A., Tiu, B. D. B.,  Adas, S., Bunge, S. D., Advincula,  R. C. “Solvatochromic, thermochromic and pH-sensory DCDHF-hydrazone molecular switch: response to alkaline analytes” RSC Advances, 2016 6, 102296-102305.  
6. Laali*, K. K., Rathman, B. M., Bunge, S. D., Qi, X., Borosky, G. L. “Fluoro-curcuminoids and curcuminoid-BF2 adducts: Synthesis, X-ray structures, bioassay, and computational/docking study.” Journal of Fluorine Chemistry, 2016 191, 29-41.  
7. Tandon*, S. S.; Bunge, S. D.; Toth, S. A.; Sanchiz, J.; Thompson, L. K.; Shelley, J. T. “Antiferromagnetically Coupled Dimeric Dodecacopper Supramolecular Architectures of Macrocyclic Ligands with a Symmetrical μ6- BO33- Central Moiety” Inorganic Chemistry, 2015 54(14) 6873-6884.  
8. Laali*, K. K., Insuasty, D., Abonia, R., Insuasty, B., Bunge, S. D. “Novel quinoline-imidazolium adducts via the reaction of 2-oxoquinoline-3-carbaldehyde and quinoline-3-carbaldehydes with 1-butyl-3-methylimidazolium chloride [BMINI][Cl]” Tetrahedron Letters, 2014 55(31) 4395-4399.  
9. Anwar, M. U., Dawe, L. N., Parsons, S. R., Tandon, S. S., Thompson*, L. K., Dey, S. K., Mereacre, V. Reiff, W. M., Bunge, S. D. “Oligonuclear Fe complexes (Fe, Fe4, Fe6, Fe9) Derived from Tritopic Pyridine Bis-hydrazone Ligands - Structural, Magnetic, and Mossbauer Studies” Inorganic Chemistry, 2014, 53(9), 4655-4668.  
10. Laali*, K. K., Ganesh, C. Bunge, S. D. “Selectfluor-mediated mild oxidative halogenation and thiocyanation of 1-aryl-allenes with TMSX (X = Cl, Br, I, NCS) and NH4SCN” Nandi, Tetrahedron Letters, 2014  55(15), 2401-2405.   
11. Okazaki, T., Laali, K. K.*, Bunge, S. D., Adas, S. K. “4-(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry” European Journal of Organic Chemistry, 2014, 8, 1630-1644.  
12. Adas, S. K., Ocana, J. A., Bunge, S. D.*, “Synthesis and Structural Characterization of a Series of Group 11 2,2-Dialkyl-1,3-dicyclohexylguanidinate Complexes” Australian Journal of Chemistry, 2014, 67(7), 1021-1029. 
13. Getmanenko, Y. A., Kang, S. W., Shakya, N., Pokhrel, C., Bunge, S. D., Kumar, S., Ellman, B. D., Twieg, R. J.*, “Bis(5-alkylthiophen-2-yl)arene Liquid Crystals as Molecular Semiconductors”  Journal of Materials Chemistry C, 2014, 2(14), 2600-2611.  
14. Getmanenko, Y. A., Kang, S. W., Shakya, N., Pokhrel, C., Bunge, S. D., Kumar, S., Ellman, B. D., Twieg, R. J.,* “5,5'-Bis-(alkylpyridinyl)-2,2'-bithiophenes: synthesis, liquid crystalline behaviour and charge transport”  Journal of Materials Chemistry C, 2014, 2(2), 256-271.  
15. Pearson, A. J.*, Panda, S., Bunge, S. D., “Synthesis of a Potential Intermediate for TMC-95A via an Organocatalyzed Aldol Reaction” Journal of Organic Chemistry, 2013, 78(19), 9921-9928.  
16. Fouad, F.*, Ellman, B., Bunge, S., Miller, P. Twieg, R.,“Liquid Crystalline Symmetrical 3,6-Diaryl-1,2,4,5-Tetrazines” Molecular Crystals and Liquid Crystals 2013, 582(1), 34-42.
17. Anwar, M. U. Dawe, L. N., Tandon, S. S.*, Bunge, S. D., Thompson, L. K.*, “Polynuclear lanthanide (Ln) complexes of a tri-functional hydrazone ligand - mononuclear (Dy), dinuclear (Yb, Tm), tetranuclear (Gd), and hexanuclear (Gd, Dy, Tb) examples” Dalton Transactions 2013, 42(21), 7781-7794.  
18. Fouad, F., Bunge, S. D*, Twieg, R. J. “Tetranaphthyleno[5,6-bcd:11,2-b'c'd':17,18-b'' c''d'':23,24-b''c'''d''']tetrafuran” Acta Cryst. Sec. C-Crystal Structure Communications 2012, 68, O465.  
19. Tandon, S. S.*, Bunge, S. D., Sanchiz, J, Thompson, L. K., “Structures and Magnetic Properties of an Antiferromagnetically Coupled Polymeric Copper(II) Complex and Ferromagnetically Coupled Hexanuclear Nickel(II) Clusters” Inorganic Chemistry  2012 51(5) 3270-3282  
20. Getmanenko, Y. A., Hales, J. M., Balu, M., Fu, J., Zojer, E., Kwon, O., Mendez, J., Thayumanavan, S., Walker, G., Zhang, Q., Bunge, S. D., Bredas, J. L., Hagan, D. J., Van Stryland, E. W., Barlow, S., Marder S. R.* “Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR” Journal of Materials Chemistry 2012 22(10) 4371-4382.