Structural criteria for the design of anion receptors: Incorporating the anion-π interaction

ORGN 379

Orion B. Berryman, oberryma@uoregon.edu1, David P. Stay1, Darren W. Johnson, dwj@uoregon.edu1, Vyacheslav Bryantsev, vyacheslav.bryantsev@pnl.gov2, and Benjamin P. Hay, haybp@ornl.gov3. (1) Department of Chemistry and Materials Science Institute, University of Oregon, Eugene, OR 97403, (2) Chemical Sciences Division, Pacific Northwest National Laboratory, PO Box 999, Richland, WA 99352, (3) Chemical Sciences Division, Oak Ridge National Laboratory, PO BOX 2008, Oak Ridge, TN 37831-6119
The anion–π interaction is a noncovalent attractive interaction between an anion and an electron-deficient π–system that has received recent attention. It has been reported that this interaction can be used in the design of anion receptors. A complication in designing receptors that utilize this interaction is that theoretical predictions of the geometry do not always correlate to structures reported in the CSD. This presentation addresses both the incorporation of the anion–π interaction into receptors, as well as the preferred binding geometry for the interaction. Association constants are provided illustrating the influence of the anion–π interaction in solution. Molecular structures derived from single crystal X–ray diffraction (1,2,4,5–tetracyanobenzene•Br– below, left) and electronic calculations at the MP2/aug–cc–pVDZ level of theory (1,2,4,5–tetracyanobenzene•halide below, right) are provided that predict an off center binding geometry for the anion–π interaction.

 

Molecular Recognition and Self-Assembly
8:00 AM-12:00 PM, Tuesday, 12 September 2006 Moscone Center -- Room 132, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006