Cooperativity in Hydrogen-Bonded Macrocycles Derived from Nucleobases

David Almacellas; Stephanie C.C. van der Lubbe; Alice A. Grosch; Iris Tsagri; Pascal Vermeeren; Célia Fonseca Guerra; Jordi Poater

doi:10.1002/ejoc.202301164

Cooperativity in Hydrogen-Bonded Macrocycles Derived from Nucleobases

David Almacellas
, Stephanie C.C. van der Lubbe
, Alice A. Grosch
, Iris Tsagri
, Pascal Vermeeren^*
, Célia Fonseca Guerra^*
, Jordi Poater^*

^*Corresponding author for this work

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

Abstract

Introducing a rigid linear π-conjugated acetylene linker into a supramolecular building block consisting of a hydrogen-bond donor side and a hydrogen-bond acceptor side yields a decrease in cooperativity in the resulting formed quartet. This follows from our Kohn-Sham molecular orbital and Voronoi deformation density analyses of hydrogen-bonded macrocycles based on guanine and cytosine nucleobases. The acetylene linker abstracts electron density from the hydrogen-bond acceptor and donor, making the hydrogen-bond acceptor more negatively charged and the hydrogen-bond donor more positively charged and hence suppressing the donor–acceptor charge transfer interaction between the interacting fragments. This, ultimately, hampers the cooperativity in the hydrogen-bonded macrocycle. We envision that these findings could open the door to new design principles for the development of novel hydrogen-bond supramolecular macrocycles.

Original language	English
Article number	e202301164
Journal	European Journal of Organic Chemistry
Volume	27
Issue number	19
DOIs	https://doi.org/10.1002/ejoc.202301164
Publication status	Published - 21 May 2024

Bibliographical note

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

Funding

D.A. is grateful to the Ministerio de Ciencia e Innovaci\u00F3n for the PRE2018-084044 fellowship. J.P. thanks the Spanish MINECO (PID2019-106830GB-I00, PID2022-138861NB-I00, and CEX2021-001202-M) and the Generalitat de Catalunya (2021SGR442). P.V. and C.F.G. acknowledge the financial support from the Netherlands Organization for Scientific Research (NWO).

Funders	Funder number
Ministerio de Ciencia e Innovación
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CEX2021-001202-M, PID2019-106830GB-I00, PID2022-138861NB-I00
Generalitat de Catalunya	2021SGR442

Keywords

Cooperativity
Density Functional Theory
Energy Decomposition Analysis
Hydrogen Bonds
Self-Assembly

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10.1002/ejoc.202301164

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title = "Cooperativity in Hydrogen-Bonded Macrocycles Derived from Nucleobases",

abstract = "Introducing a rigid linear π-conjugated acetylene linker into a supramolecular building block consisting of a hydrogen-bond donor side and a hydrogen-bond acceptor side yields a decrease in cooperativity in the resulting formed quartet. This follows from our Kohn-Sham molecular orbital and Voronoi deformation density analyses of hydrogen-bonded macrocycles based on guanine and cytosine nucleobases. The acetylene linker abstracts electron density from the hydrogen-bond acceptor and donor, making the hydrogen-bond acceptor more negatively charged and the hydrogen-bond donor more positively charged and hence suppressing the donor–acceptor charge transfer interaction between the interacting fragments. This, ultimately, hampers the cooperativity in the hydrogen-bonded macrocycle. We envision that these findings could open the door to new design principles for the development of novel hydrogen-bond supramolecular macrocycles.",

keywords = "Cooperativity, Density Functional Theory, Energy Decomposition Analysis, Hydrogen Bonds, Self-Assembly",

author = "David Almacellas and \{van der Lubbe\}, \{Stephanie C.C.\} and Grosch, \{Alice A.\} and Iris Tsagri and Pascal Vermeeren and \{Fonseca Guerra\}, C{\'e}lia and Jordi Poater",

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AU - Almacellas, David

AU - van der Lubbe, Stephanie C.C.

AU - Grosch, Alice A.

AU - Tsagri, Iris

AU - Vermeeren, Pascal

AU - Fonseca Guerra, Célia

AU - Poater, Jordi

PY - 2024/5/21

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N2 - Introducing a rigid linear π-conjugated acetylene linker into a supramolecular building block consisting of a hydrogen-bond donor side and a hydrogen-bond acceptor side yields a decrease in cooperativity in the resulting formed quartet. This follows from our Kohn-Sham molecular orbital and Voronoi deformation density analyses of hydrogen-bonded macrocycles based on guanine and cytosine nucleobases. The acetylene linker abstracts electron density from the hydrogen-bond acceptor and donor, making the hydrogen-bond acceptor more negatively charged and the hydrogen-bond donor more positively charged and hence suppressing the donor–acceptor charge transfer interaction between the interacting fragments. This, ultimately, hampers the cooperativity in the hydrogen-bonded macrocycle. We envision that these findings could open the door to new design principles for the development of novel hydrogen-bond supramolecular macrocycles.

AB - Introducing a rigid linear π-conjugated acetylene linker into a supramolecular building block consisting of a hydrogen-bond donor side and a hydrogen-bond acceptor side yields a decrease in cooperativity in the resulting formed quartet. This follows from our Kohn-Sham molecular orbital and Voronoi deformation density analyses of hydrogen-bonded macrocycles based on guanine and cytosine nucleobases. The acetylene linker abstracts electron density from the hydrogen-bond acceptor and donor, making the hydrogen-bond acceptor more negatively charged and the hydrogen-bond donor more positively charged and hence suppressing the donor–acceptor charge transfer interaction between the interacting fragments. This, ultimately, hampers the cooperativity in the hydrogen-bonded macrocycle. We envision that these findings could open the door to new design principles for the development of novel hydrogen-bond supramolecular macrocycles.

KW - Cooperativity

KW - Density Functional Theory

KW - Energy Decomposition Analysis

KW - Hydrogen Bonds

KW - Self-Assembly

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Cooperativity in Hydrogen-Bonded Macrocycles Derived from Nucleobases

Abstract

Bibliographical note

Funding

Keywords

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