Cooperativity in Hydrogen-Bonded Macrocycles Derived from Nucleobases
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 d...
| Autores: | , , , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2024 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositório: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/218759 |
| Acesso em linha: | https://hdl.handle.net/2445/218759 |
| Access Level: | Acceso aberto |
| Palavra-chave: | Hidrogen ADN Química supramolecular Hydrogen DNA Supramolecular chemistry |
| Resumo: | 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. |
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