Arenediazonium Salts as Versatile (meso-Ionic) Tectons. Charge-Transfer Intercalates and Clathrates in Unusual Crystalline Networks Self-Assembled with Neutral Aromatic π-Donors

Authors

Sergey Lindeman, Marquette UniversityFollow
Jay K. Kochi, University of Houston

Document Type

Article

Language

eng

Publication Date

5-1-2004

Publisher

American Chemical Society

Source Publication

Crystal Growth and Design

Source ISSN

1528-7483

Abstract

Synopsis

Arenediazonium salts as tectonic building elements for crystal engineering possess a unique array of binding properties, including (a) strong acceptor affinity toward electronegative or neutral σ-donors; (b) enhanced C−H acidity for extensive formation of C−H···X bonds; and (c) π-acceptor properties of the electron-deficient arene substituent for charge-transfer complex formation with appropriate aromatic π-donors. Shown: Donor/acceptor intercalate in the layered structure of 3,5(NO₂)C₆H₃N₂⁺ BF₄^- with naphthalene.

Abstract

The surprisingly uniform crystal packings of various arenediazonium salts (ArN₂⁺X^-) largely consist of two-dimensional ionic layers from various (N₂⁺···X^-) interactions coupled with a series of antiparallel arrays of pendant aryl groups (Ar). This crystalline architecture can be deliberately modified by the introduction of different (neutral) aromatic π-donors. On the basis of the exceptional electron-acceptor strength of the (N₂⁺) group, the principal crystal-forming interactions of the arenediazonium tecton can be dissected into (a) strong coordination to anionic and electron-rich (neutral) σ-donors within the equatorial plane, (b) enhanced capacity for (C−H···X) hydrogen bonding, and (c) remarkable aptitude to form (noncovalent) charge-transfer bonds with aromatic π-donors. Thus, the detailed analysis of crystalline networks found in 3,5-dinitro and 4-carboethoxy derivatives of benzenediazonium salts recognizes them as remarkable intercalate and clathrate structures in which various charge-transfer interactions between the electron-deficient arene moiety and aromatic π-donors are essential for the stabilization of the unusual layered/network structures.

Comments

Accepted version. Crystal Growth & Design, Vol. 4, No. 3 (2004): 563-571. DOI. © 2004 American Chemical Society. Used with permission.

Dr. Sergey V. Lindeman was associated with University of Houston at the time of publication.

Recommended Citation

Lindeman, Sergey and Kochi, Jay K., "Arenediazonium Salts as Versatile (meso-Ionic) Tectons. Charge-Transfer Intercalates and Clathrates in Unusual Crystalline Networks Self-Assembled with Neutral Aromatic π-Donors" (2004). Chemistry Faculty Research and Publications. 581.
https://epublications.marquette.edu/chem_fac/581