Inorganic/Organic Materials Chemistry, Chemical History

Materials Research
Our research focuses on synthetic approaches to unique π-conjugated systems to produce materials with improved optical and electronic properties. Conjugated polymers are of considerable fundamental and technological interest due to a wide variety of potential applications, including their use in batteries, sensors, electrochromic devices, LEDs, and field effect transistors. Presently, we are studying a variety of nitrogen-derivatized polythiophene-based systems as potential low bandgap materials. These systems include polythieno[3,4-b]pyrazines, polyalkylaminothiophenes, and polythienopyrroles (Figure 1).

Figure 1. Poly(2,3-dialkylthieno[3,4-b]pyrazine) (A), polyalkylaminothiophene (B), and N-functionalized poly(dithieno[3,2-b:2',3'-d]pyrrole) (C).

In addition to producing conjugated polymers with reduced band gaps and lower oxidation potentials, another goal is to utilize the binding ability of the nitrogen functionalities to produce metallated polymeric materials (Figure 2). Such materials would combine the electro- and photochemical properties of classical transition metal coordination complexes with the electronic and optical properties of conjugated organic polymers. The combined attributes of these hybrid polymeric systems should provide materials that are of interest for the design of donor-acceptor conjugated systems utilizing inorganic sites as both donors and acceptors, as well as serving as electro- or photosensitive switches. In addition, heterometallic polymers could act as “push-pull” compounds which are of particular interest for the design of nonlinear optical materials.

Figure 2. A metallated polythieno[3,4-b]pyrazine

Students working on these projects gain experience in organic, inorganic, and polymer synthesis, as well as gain experience with a variety of spectroscopic and electrochemical techniques.

Chemical History
My main historical focus is the incorporation of chemical history into the chemical curriculum. During the last few decades, there has been a growing awareness regarding the important role played by the teaching of the History of Science in undergraduate and graduate science courses. Over the years various authors have given sound justification for the inclusion of a historical component in science programs. As applied to chemistry, these include that:

• History promotes better comprehension of scientific concepts and methods.
• History illustrates the importance of individual thought and creativity in the development of science.
• History is necessary to understand the nature of science.
• History counteracts the dogmatic view of science commonly found in texts and classes.
• History humanizes the subject matter of science, making it less abstract and more engaging for students.
• History shows the connections between chemical disciplines.
• History allows one to more easily identify and confront pseudoscience.

Specific historical projects include research on the history and genealogy of the NDSU chemistry department, the biography of Edwin Ladd, and research on glass technology of the 1400s.

Selected Publications

Li Wen, Jon P. Nietfeld, Chad M. Amb, and Seth C. Rasmussen "New Tunable Thieno[3,4-b]pyrazine-based Materials," Synthetic Metals 2009, 159, in press.

Chad M. Amb and Seth C. Rasmussen "Synthesis and Characterization of a New p-Extended Nickel Dithiolene Complex for Molecular Materials," Synthetic Metals 2009, 159, in press.

Chad M. Amb and Seth C. Rasmussen "Synthesis and Structural Characterization of Thiophene-functionalized Metal Dithiolenes" In Chemical Crystallography, Columbus, F., Ed.; NOVA Publishers: Hauppauge, NY, to be published 2009.

Maocheng Yan, Dennis E. Tallman, Seth C. Rasmussen, and Gordon P. Bierwagen "Neutral and n-Doped Conjugated Polymers for Corrosion Control of Aluminum Alloys," Journal of the Electrochemical Society 2009, 156,
C360-C366.

Jon P. Nietfeld, Sean J. Evenson, Li Wen, and Seth C. Rasmussen "Application of Tunable Thieno[3,4-b]pyrazine Building Blocks to New Low Band Gap Materials," Polymer Preprints 2009, 50(1), 503-504.

Maocheng Yan, Jie He, Dennis E. Tallman, Seth C. Rasmussen, and Gordon P. Bierwagen "Neutral and n-Doped Conjugated Polymers for Corrosion Control of Aluminum Alloys," ECS Transactions 2008, 16(52), 183-194.

Li Wen, Jon P. Nietfeld, Chad M. Amb, and Seth C. Rasmussen "Synthesis and Characterization of New 2,3-Disubstituted Thieno[3,4-b]pyrazines: Tunable Building Blocks for Low Band Gap Conjugated Materials," Journal of Organic Chemistry 2008, 73, 8529-8536.

Seth C. Rasmussen "Bruce T. Moran's Distilling Knowledge: Alchemy, Chemistry, and the Scientific Revolution and Andreas Libavius and the Transformation of Alchemy" Bulletin for the History of Chemistry 2008, 33, 122-123 (Book Reviews).

Li Wen, Jon P. Nietfeld, Chad M. Amb, and Seth C. Rasmussen "New Tunable Thieno[3,4-b]pyrazine Building Blocks and Their Application to Low Band Gap Materials," Polymer Preprints 2008, 49(2), 633-634.

Seth C. Rasmussen, Carmen J. Giunta, and Misty R. Tomchuk "Content Standards for the History and Nature of Science," in Chemistry in the National Science Education Standards: Models for Meaningful Learning, 2nd Ed., Bretz, S. L., Ed.; American Chemical Society: Washington, DC, 2008; Chapter 9.

Li Wen, Benjamin C. Duck, Paul C. Dastoor, and Seth C. Rasmussen "Poly(2,3-dihexylthieno[3,4-b]pyrazine) via GRIM Polymerization: The Simple Preparation of a Solution Processable, Low Band Gap Conjugated Polymer," Macromolecules 2008, 41, 4576-4578.

Ted M. Pappenfus, Bethany J. Hermanson, Tyler J. Helland, Garett G. W. Lee, Steven M. Drew, Kent R. Mann, Kari A. McGee, and Seth C. Rasmussen "Reduced Band Gap Dithieno[3,2-b:2',3'-d]pyrroles: n-Type Organic Materials via Unexpected Reactivity," Organic Letters 2008, 10, 1553-1556.

Seth C. Rasmussen "Advances in 13th Century Glass Manufacturing and their Effect on Chemical Progress," Bulletin for the History of Chemistry 2008, 33, 28-34.

Jon P. Nietfeld, Christopher L. Heth, and Seth C. Rasmussen "Poly(acenaphtho[1,2-b]thieno[3,4-e]pyrazine): A New Low Band Gap Conjugated Polymer," Chemical Communications 2008, 981-983.

Chad M. Amb and Seth C. Rasmussen "Sterics vs. Electronics: Regioselective Cross-coupling of Polybrominated Thiophenes," European Journal of Organic Chemistry 2008, 801-804.      

Li Wen and Seth C. Rasmussen "Synthesis and Structural Characterization of 2,5-Dihalo-3,4-dinitrothiophenes," Journal of Chemical Crystallography 2007, 37, 387-398.

Seth C. Rasmussen "The History of Science as a Tool to Identify and Confront Pseudoscience," Journal of Chemical Education 2007, 84, 949-951.

Seth C. Rasmussen, Katsu Ogawa, and Scott D. Rothstein "Synthetic Approaches to Band Gap Control in Conjugated Polymeric Materials," in the Handbook of Organic Electronics and Photonics, Nalwa, H. S., Ed.; American
Scientific Publishers: Stevenson Ranch, CA, 2007; Vol. 1, Chapter 1.

Seth C. Rasmussen and Martin Pomerantz "Low Bandgap Conducting Polymers," in Conjugated Polymers: Theory, Synthesis, Properties, and Characterization, Skotheim, T. A., Reynolds, J. R., Eds.; Handbook of Conducting Polymers, 3rd Ed.; CRC Press: Boca Raton, FL, 2007; Chapter 12.