Anion Recognition by Pyrylium Cations and Thio-, Seleno- and Telluro- Analogues: A Combined Theoretical and Cambridge Structural Database Study

Molecules

David Quiñonero¹ 

[1] Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca, Spain; E-Mail

关键词: chalcogen bond;    anion-π interaction;    noncovalent interactions;    pyrylium complexes;    anion recognition;    DFT;   

DOI  :  10.3390/molecules200711632

来源: mdpi

【 摘 要 】

Pyrylium salts are a very important class of organic molecules containing a trivalent oxygen atom in a six-membered aromatic ring. In this manuscript, we report a theoretical study of pyrylium salts and their thio-, seleno- and telluro- analogues by means of DFT calculations. For this purpose, unsubstituted 2,4,6-trimethyl and 2,4,6-triphenyl cations and anions with different morphologies were chosen (Cl^–, NO₃^– and BF₄^–). The complexes were characterized by means of natural bond orbital and “atoms-in-molecules” theories, and the physical nature of the interactions has been analyzed by means of symmetry-adapted perturbation theory calculations. Our results indicate the presence of anion-π interactions and chalcogen bonds based on both σ- and π-hole interactions and the existence of very favorable σ-complexes, especially for unsubstituted cations. The electrostatic component is dominant in the interactions, although the induction contributions are important, particularly for chloride complexes. The geometrical features of the complexes have been compared with experimental data retrieved from the Cambridge Structural Database.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.