title: Competition Between π-π and C-H/π Interactions: A Comparison of the Structural and Electronic Properties of Alkoxy-Substituted 1,8-Bis((propyloxyphenyl)ethynyl)naphthalenes.
abstract: The structural and electronic consequences of π-π and C-H/π interactions in two alkoxy-substituted 1,8-bis- ((propyloxyphenyl)ethynyl)naphthalenes are explored by using X-ray crystallography and electronic structure computations. The crystal structure of analogue 4, bearing an alkoxy side chain in the 4-position of each of the phenyl rings, adopts a π-stacked geometry, whereas analogue 8, bearing alkoxy groups at both the 2- and the 5-positions of each ring, has a geometry in which the rings are splayed away from a π-stacked arrangement. Symmetry-adapted perturbation theory analysis was performed on the two analogues to evaluate the interactions between the phenylethynyl arms in each molecule in terms of electrostatic, steric, polarization, and London dispersion components. The computations support the expectation that the π-stacked geometry of the alkoxyphenyl units in 4 is simply a consequence of maximizing π-π interactions. However, the splayed geometry of 8 results from a more subtle competition between different noncovalent interactions: this geometry provides a favorable anti-alignment of C-O bond dipoles, and two C-H/π interactions in which hydrogen atoms of the alkyl side chains interact favorably with the π electrons of the other phenyl ring. These favorable interactions overcome competing π-π interactions to give rise to a geometry in which the phenylethynyl substituents are in an offset, unstacked arrangement.
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452.
authors.forename: Bradley E
authors.initials: BE
authors.lastname: Carson
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452.|Center for Computational Molecular Science and Technology, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA).
authors.forename: Trent M
authors.initials: TM
authors.lastname: Parker
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452.|Center for Computational Molecular Science and Technology, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA).
authors.forename: Edward G
authors.initials: EG
authors.lastname: Hohenstein
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452.
authors.forename: Glen L
authors.initials: GL
authors.lastname: Brizius
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452.
authors.forename: Whitney
authors.initials: W
authors.lastname: Komorner
authors.affiliation: Department of Chemistry, Bethel University, St. Paul, MN 55112 (USA).
authors.forename: Rollin A
authors.initials: RA
authors.lastname: King
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452. david.collard@chemistry.gatech.edu.
authors.forename: David M
authors.initials: DM
authors.lastname: Collard
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA), Fax: (+1) 404-894-7452. sherrill@gatech.edu.|Center for Computational Molecular Science and Technology, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332-0400 (USA). sherrill@gatech.edu.|School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (USA). sherrill@gatech.edu.
authors.forename: C David
authors.initials: CD
authors.lastname: Sherrill
keywords: density functional calculations; noncovalent interactions; pi interactions; stacking interactions; substituent effects