Redox modulation of two and three-electron accepting imide systems with alkyl thioureas

ORGN 14

Joseph B. Carroll1, Mark Gray2, Kathryn A. McMenimen3, Darren G. Hamilton3, and Vincent Rotello4. (1) Department of Chemistry, University of Massachusetts-Amherst, Amherst, MA 01003, (2) Department of Chemistry, University of Massachusetts, Amherst, MA 01003, (3) Department of Chemistry, Mount Holyoke College, South Hadley, MA 01075, (4) Department of Chemistry, University of Massachusetts Amherst, Amherst, MA 01003
The ability to control the strengths of association through simple redox modulation is a powerful tool in the search for new, electronically controlled supramolecular components. Mellitic triimides (1) undergo three sequential one-electron reduction processes whose potentials are significantly lowered in the presence of alkyl thioureas. Similar hydrogen bond-mediated stabilization of reduced forms is observed with structurally related benzene diimides with the capacity to accept up to two electrons. Theoretical, computational investigations allow for calculation of the relative association constants between the different electronic states of the imide acceptors and thioureas, indicating a dramatic strengthening of the hydrogen bound imide/thiourea complex with increasing acceptor charge density.

 

Molecular Recognition and Self-Assembly
8:20 AM-12:00 PM, Sunday, September 7, 2003 Sheraton New York -- Imperial Ballroom B, Oral

Division of Organic Chemistry
The 226th ACS National Meeting, New York, NY, September 7-11, 2003