Cooperative Self-Assembly in Linear Chains Based on Halogen Bonds

P. Vermeeren, L.P. Wolters, G. Paragi, C. Fonseca Guerra

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

© 2021 The Authors. ChemPlusChem published by Wiley-VCH GmbHCooperative properties of halogen bonds were investigated with computational experiments based on dispersion-corrected relativistic density functional theory. The bonding mechanism in linear chains of cyanogen halide (X−CN), halocyanoacetylene (X−CC−CN), and 4-halobenzonitrile (X−C6H4−CN) were examined for X = H, Cl, Br, and I. Our energy decomposition and Kohn-Sham molecular-orbital analyses revealed the bonding mechanism of the studied systems. Cyanogen halide and halocyanoacetylene chains possess an extra stabilizing effect with increasing chain size, whereas the 4-halobenzonitrile chains do not. This cooperativity can be traced back to charge separation within the σ-electronic system by charge-transfer between the lone-pair orbital of the nitrogen (σHOMO) on one unit and the acceptor orbital of the C−X (σ*LUMO) on the adjacent unit. As such, the HOMO-LUMO gap in the σ-system decreases, and the cooperativity increases with chain length revealing the similarity in the bonding mechanisms of hydrogen and halogen bonds.
Original languageEnglish
Pages (from-to)812-819
JournalChemPlusChem
Volume86
Issue number6
DOIs
Publication statusPublished - 1 Apr 2021

Funding

We gratefully acknowledge the financial support from the Netherlands Organization for Scientific Research NWO (ECHO), Dutch Astrochemistry Network (DAN), and the Marie Curie Intra European Fellowship within the 7 European Community Framework Programme. th We gratefully acknowledge the financial support from the Netherlands Organization for Scientific Research NWO (ECHO), Dutch Astrochemistry Network (DAN), and the Marie Curie Intra European Fellowship within the 7th European Community Framework Programme.

FundersFunder number
Dutch Astrochemistry Network
Netherlands Organization for Scientific Research NWO
Seventh Framework Programme

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