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Cyclic networks of halogen‐bonding interactions in molecular self‐assemblies: a theoretical N— X …N versus C— X …N investigation
Author(s) -
Parra Ruben D.,
Castillo Álvaro
Publication year - 2017
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520617002335
Subject(s) - halogen bond , intramolecular force , natural bond orbital , lone pair , crystallography , halogen , chemistry , cooperativity , atom (system on chip) , density functional theory , hydrogen bond , computational chemistry , molecule , stereochemistry , organic chemistry , alkyl , biochemistry , computer science , embedded system
The geometries and energetics of molecular self‐assembly structures that contain a sequential network of cyclic halogen‐bonding interactions are investigated theoretically. The strength of the halogen‐bonding interactions is assessed by examining binding energies, electron charge transfer (NBO analysis) and electron density at halogen‐bond critical points (AIM theory). Specifically, structural motifs having intramolecular N— X …N ( X = Cl, Br, or I) interactions and the ability to drive molecular self‐assembly via the same type of interactions are used to construct larger self‐assemblies of up to three unit motifs. N— X …N halogen‐bond cooperativity as a function of the self‐assembly size, and the nature of the halogen atom is also examined. The cyclic network of the halogen‐bonding interactions provides a suitable cavity rich in electron density (from the halogen atom lone pairs not involved in the halogen bonds) that can potentially bind an electron‐deficient species such as a metal ion. This possibility is explored by examining the ability of the N— X …N network to bind Na + . Likewise, molecular self‐assembly structures driven by the weaker C— X …N halogen‐bonding interactions are investigated and the results compared with those of their N— X …N counterparts.