A1 Journal article (refereed)
Short X···N Halogen Bonds With Hexamethylenetetraamine as the Acceptor (2021)

Anyfanti, G., Bauzá, A., Gentiluomo, L., Rodrigues, J., Portalone, G., Frontera, A., Rissanen, K., & Puttreddy, R. (2021). Short X···N Halogen Bonds With Hexamethylenetetraamine as the Acceptor. Frontiers in Chemistry, 9, Article 623595. https://doi.org/10.3389/fchem.2021.623595

JYU authors or editors

Publication details

All authors or editors: Anyfanti, Goulielmina; Bauzá, Antonio; Gentiluomo, Lorenzo; Rodrigues, João; Portalone, Gustavo; Frontera, Antonio; Rissanen, Kari; Puttreddy, Rakesh

Journal or series: Frontiers in Chemistry

eISSN: 2296-2646

Publication year: 2021

Publication date: 29/04/2021

Volume: 9

Article number: 623595

Publisher: Frontiers Media SA

Publication country: Switzerland

Publication language: English

DOI: https://doi.org/10.3389/fchem.2021.623595

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/75287


Hexamethylenetetramine (HMTA) and N-haloimides form two types of short (imide)X···N and X–X···N (X = Br, I) halogen bonds. Nucleophilic substitution or ligand-exchange reaction on the peripheral X of X–X···N with the chloride of N-chlorosuccinimide lead to Cl–X···N halogen-bonded complexes. The 1:1 complexation of HMTA and ICl manifests the shortest I···N halogen bond [2.272(5) Å] yet reported for an HMTA acceptor. Two halogen-bonded organic frameworks are prepared using 1:4 molar ratio of HMTA and N-bromosuccinimide, each with a distinct channel shape, one possessing oval and the other square grid. The variations in channel shapes are due to tridentate and tetradentate (imide)Br···N coordination modes of HMTA. Density Functional Theory (DFT) studies are performed to gain insights into (imide)X···N interaction strengths (ΔEint). The calculated ΔEint values for (imide)Br···N (−11.2 to −12.5 kcal/mol) are smaller than the values for (imide)I···N (−8.4 to −29.0 kcal/mol). The DFT additivity analysis of (imide)Br···N motifs demonstrates Br···N interaction strength gradually decreasing from 1:1 to 1:3 HMTA:N-bromosuccinimide complexes. Exceptionally similar charge density values ρ(r) for N–I covalent bond and I···N non-covalent bond of a (saccharin)N–I···N motif signify the covalent character for I···N halogen bonding.

Keywords: chemical bonds; halogens; organic compounds; supramolecular chemistry

Free keywords: halogen bond; hexamethylenetetraamine; HMTA; N-haloimide; dihalogen; interhalogen

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Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 1

Last updated on 2022-14-09 at 12:00