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...
| Authors: | ; ; ; ; ; |
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| Format: | Article |
| Status: | Published version |
| Publication date: | 2024 |
| Country: | España |
| Institution: | Universidad de Barcelona |
| Repository: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/218759 |
| Online Access: | https://hdl.handle.net/2445/218759 |
| Access Level: | Open access |
| Keyword: | Hidrogen ADN Química supramolecular Hydrogen DNA Supramolecular chemistry |
| Summary: | 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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