Cooperative Self‐Assembly in Linear Chains Based on Halogen Bonds
ChemPlusChem, vol. 86, pp. 812–819
Abstract
Abstract Cooperative 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.
Authors 4
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Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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Gábor Paragi corresponding
Hungarian Research Network · University of Pecs · Vrije Universiteit Amsterdam
Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Institute of Physics University of Pécs Ifjúság útja 6 7624 Pécs Hungary
MTA-SZTE Biomimetic Systems Research Group Eötvös Loránd Research Network (ELKH) Dóm tér 8 6720 Szeged Hungary
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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Célia Fonseca Guerra corresponding Aachen Leiden Institute of Chemistry Leiden Institute of Chemistry, Gorlaeus Laboratories
Leiden University · Vrije Universiteit Amsterdam
Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Leiden Institute of Chemistry, Gorlaeus Laboratories Leiden University Einsteinweg 55 2333 CC Leiden The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands
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