Structural criteria for the design of anion receptors: The interaction of halides with electron-deficient arenes

Journal Article · Mon Jan 01 00:00:00 EST 2007 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja063460m· OSTI ID:1098193

Berryman, Mr. Orion B. ^[1]; Bryantsev, Vyacheslav S. ^[2]; Stay, Mr. David P. ^[1]; Johnson, Prof. Darren W. ^[1]; Hay, Benjamin ^[3]

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1. University of Oregon
2. California Institute of Technology, Pasadena
3. ORNL

This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (i) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (ii) evaluation of crystal structures found in the Cambridge Structural Database, and (iii) MP2/aug-cc-pVDZ calculations of F-, Cl-, and Br- complexes with TCB, 1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the pi system, the results establish that three distinctly different types of complexes are possible: strongly covalent sigma complexes, weakly covalent donor-pi-acceptor complexes, and noncovalent anion-pi complexes. When aryl C-H groups are present, a fourth type of interaction leads to C-H center dot center dot center dot X- hydrogen bonding. Characterization of the different geometries encountered with the four possible binding motifs provides criteria needed to design host architectures containing electron-deficient arenes.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: DE-AC05-00OR22725
• OSTI ID: 1098193
• Journal Information: Journal of the American Chemical Society, Vol. 129, Issue 1; ISSN 0002--7863
• Country of Publication: United States
• Language: English