Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Celine Nieuwland; Siebe Lekanne Deprez; Claris de Vries; Célia Fonseca Guerra

doi:10.1002/chem.202300850

Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Celine Nieuwland, Siebe Lekanne Deprez, Claris de Vries, Célia Fonseca Guerra^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.

Original language	English
Article number	e202300850
Number of pages	7
Journal	Chemistry - A European Journal
Volume	29
Issue number	34
Early online date	28 Mar 2023
DOIs	https://doi.org/10.1002/chem.202300850
Publication status	Published - 19 Jun 2023

Bibliographical note

Funding Information:
The authors thank Mees Kuipers for exploring the viability of this project and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Funding

The authors thank Mees Kuipers for exploring the viability of this project and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. The authors thank Mees Kuipers for exploring the viability of this project and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative.

Funders	Funder number
SURF Cooperative
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

amides
chalcogens
chemical bonding
hydrogen bonding
supramolecular polymers

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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title = "Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding",

abstract = "Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.",

keywords = "amides, chalcogens, chemical bonding, hydrogen bonding, supramolecular polymers",

author = "Celine Nieuwland and {Lekanne Deprez}, Siebe and {de Vries}, Claris and {Fonseca Guerra}, C{\'e}lia",

note = "Funding Information: The authors thank Mees Kuipers for exploring the viability of this project and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

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doi = "10.1002/chem.202300850",

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T2 - Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

AU - Nieuwland, Celine

AU - Lekanne Deprez, Siebe

AU - de Vries, Claris

AU - Fonseca Guerra, Célia

N1 - Funding Information: The authors thank Mees Kuipers for exploring the viability of this project and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. Publisher Copyright: © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

PY - 2023/6/19

Y1 - 2023/6/19

N2 - Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.

AB - Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.

KW - amides

KW - chalcogens

KW - chemical bonding

KW - hydrogen bonding

KW - supramolecular polymers

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Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

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