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Mike Tomcsi
BS Wittenberg University
KEYWORDS: Tetrathiafulvalene (TTF); Cyclophanes; Heterocycles; Molecular Recognition; Organic Conductors
Since its discovery, tetrathiafulvalene (TTF), an excellent electron donor, has been a focus of researchers. It has several interesting properties including highly reversible redox properties, ease in functionalization, and stability in a variety of environments, to name a few. These properties make TTF an excellent building block for materials chemistry. Applications including organic conductors and superconductors, chemical sensors, stations for molecular switches, rectifiers, magnetic systems, NLO materials, and photoactive systems are a sampling of the variety of TTF applications.1
In the Stoddart Group, my research has focused on TTF in several areas:
1) TTF-BASED CYCLOPHANES:
I am interested in synthesizing novel TTF-based cyclophanes for use as molecular recognition systems. This project can be divided into two areas, TTF-based and pyrroloTTF-based systems:
a) TTF-based cyclophanes:
The first class of cyclophanes is based on the parent TTF system. While there is a number or TTFphanes described in the chemical literature,2 the use of alkynes as spacers is limited. The idea of this project is to use a tetra-substituted TTF as a scaffold to create one of two different TTFphanes. The TTF moieties are spaced about 7Å apart, making this an ideal system to complex electron-poor moieties through π-π stacking. Another striking feature of these systems is the fact that these systems contain carbon and sulfur almost exclusively, which could lead to other interesting properties that place these targets on the cusp between organic and inorganic materials.
b) PyrroloTTF-based cyclophanes:
The second cyclophanes are based on pyrroloTTF. PyrroloTTF has several advantages over the parent system. The most important being the lack of cis/trans isomers that can arise from the TTF. The redox properties of pyrroloTTF are similar to that of TTF in addition to the fact that pyrroloTTF is stable to many more chemical conditions than the parent system.3 By synthesizing a variety of pyrroloTTF cyclophanes,4 an interesting, electoactive class of cyclophanes could be used in the creation of a new type of molecular switch.
2) WATER-SOLUBLE TTF DERIVATIVES:
There are two main fronts to this project:
a) Molecular recognition in H2O:
While many chemical processes involving TTF are well studied in organic media, there is little known about how many of these processes act in aqueous media, especially pure water.5 By using a series of TTF-carboxylic acids, their corresponding salts, and water-soluble CBPQT4+, we are attempting to gain an understanding of these processes and how we can eventually apply these to new systems. The acids and there salts are easily synthesized by known procedures.6
b) New H2O-soluble TTF derivatives:
An extension of the first part of this project is the rational design of new systems to be studied in aqueous media. This could be achieved through a variety of functional group transformations, in addition to varying the placement of the functional groups that will be built around the core TTF moiety. These new compounds could then be subjected to a variety of molecular recognition studies.
References
1) (a) Segura, J. L.; Martin, N. Angew. Chem. Int. Ed. 2001, 40, 1372-1409 and references therein. (b) Bryce, M. R. Adv. Mater. 1999, 11, 11-23. (c) Bryce, M. R. J. Mater. Chem. 2000, 10, 589-598.
2) (a) Matsuo, K.; Takimiya, K.; Aso, Y.; Otsubo, T.; Ogura, F. Chem. Lett. 1995, 523-524. (b) Takimiya, K.; Imamura, K.; Shibata, Y.; Aso, Y.; Ogura, F.; Otsubo, T. J. Org. Chem. 1997, 62, 5567-5574. (c) Simonsen, K. B.; Thorup, N.; Becher, J. Synthesis 1997, 1399-1404. (d) Nielsen, M. B.; Thorup, N.; Becher, J. J Chem. Soc. Perkin Trans. 1, 1998, 1305-1308.
3) Jeppesen, J. O.; Becher, J. Eur. J. Org. Chem. 2003, 3245-3266 and references therein.
4) Lau, J.; Nielsen, M. B.; Thorup, N.; Cava, M. P.; Becher, J. Eur. J. Org. Chem. 1999, 3335-3341.
5) (a) Benz, M. E.; Tabakovic, I.; Miller, L. L. Chem. Mater. 1994, 6, 351-352. (b) Patro, B.; Merrett, M. C.; Makin, S. D.; Murphy, J. A.; Parkes, K. E. B. Tetrahedron Lett. 2000, 41, 421-424. (c) Zhao, S.; Luong, J. H. T. Anal. Chim. Acta 1993, 282, 319-327.
6) (a) Yoneda, S.; Kawase, T.; Inaba, M.; Yoshida, Z. J. Org. Chem. 1978, 43, 595-598. (b) Garin, J.; Orduna, J.; Uriel, S.; Moore, A. J.; Bryce, M. R.; Wegener, S.; Yufit, D. S.; Howard, J. A. K. Synthesis 1994, 489, 493.More About Mike
Currently I am interested in heterocyclic and cyclophane chemistry and the chemistry of TTF and its derivatives. I suppose that this all can fall under the ever-growing umbrella of materials chemistry, and that's really not a bad thing. Of course sometimes I wish that I was a chemist in the 1950's, when you could say "I am going to mix water and methane and make an oak tree" and people nodded and thought that it seemed feasible. Then again, if chemistry was easy, everyone would do it.
Switching gears... I hail from the small, suburban town of Griffith, IN (http://www.griffithindiana.com). After spending the first 18 years of my existence there, I set up shop in Springfield, OH for a few years at Wittenberg University (http://www.wittenberg.edu) while I got my degree in chemistry. Then all the glitz and glamour of Hollywood and Vegas called my name and I headed out here, and have been here ever since. In the free time that I have (the time that I am not planning my wedding with my fiancée, Renee), I like to work out, play some hoops, watch movies and sports, and maybe do some 12 oz curls in the process. I also love to play various card games and take trips to Vegas to do a little gambling. Here are a couple of web pages that might be interesting:For some humorous hotel reviews in Vegas:
http://www.cheapovegas.comHere's an index of just about every card game known:
http://www.pagat.com/alpha.htmlBeing 45 min from downtown, and the fact that I have a lot of friends in the area, I figured that this works too:
http://www.chicagotribune.com/As for interesting chemistry web sites that you might want:
This is a site for IUPAC rules of nomenclature:
http://www.acdlabs.com/iupac/nomenclature/This isn't chemistry related, but it's damn humorous in a nerdy way (it's the Britney Spears guide to semiconductor physics):
http://britneyspears.ac/lasers.htm
