Competition Between π–π and CH/π Interactions: A Comparison of the Structural and Electronic Properties of Alkoxy‐Substituted 1,8‐Bis((propyloxyphenyl)ethynyl)naphthalenes |
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| Authors: | Dr. Bradley E. Carson Trent M. Parker Dr. Edward G. Hohenstein Dr. Glen L. Brizius Whitney Komorner Prof. Rollin A. King Prof. David M. Collard Prof. C. David Sherrill |
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| Affiliation: | 1. School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332‐0400 (USA), Fax: (+1) 404‐894‐7452;2. Center for Computational Molecular Science and Technology, Georgia Institute of Technology, 901 Atlantic Dr., Atlanta, GA 30332‐0400 (USA);3. Department of Chemistry, Bethel University, St. Paul, MN 55112 (USA);4. School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (USA) |
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| 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. |
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| Keywords: | density functional calculations noncovalent interactions pi interactions stacking interactions substituent effects |
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