Rapid Formation of Vinylene-Linked Covalent Organic Frameworks Promoted by Dipole Moment
Vinylene-linked covalent organic frameworks (COFs) are typically prepared via the Knoevenagel reaction under acid- or base-catalyzed solvothermal or benzoic anhydride-catalyzed solid-state conditions under reaction times spanning from 3 to 5 days. Herein, we show that the incorporation of a dipole moment into the COF building block accelerates the formation of ordered material. Under solvent-free Knoevenagel conditions, 3,8-dimethyl-4,7-phenanthroline (Phen) in combination with C<sub>3</sub>-symmetric aldehydes gives access to ordered hexagonal vinylene-linked COFs. A detailed study using triformylbenzene as counterpart evidences the formation of crystalline framework within hours. Theoretical and experimental studies indicate that the fast formation stems from favorable intermolecular interactions of the π-extended Phen building block due to the presence of a dipole moment, which also endows the material with excellent mechanical stability under ball milling. In addition, all prepared materials exhibited broad visible light absorption and narrow band gap energies of ≤2.48 eV and revealed photocatalytic activity for the degradation of dyes.
Authors
- Laura M. Salonen (ORCID: https://orcid.org/0000-0001-8194-6014)
- Tania Prieto (ORCID: https://orcid.org/0009-0005-3517-0901)
- Laura Estévez (ORCID: https://orcid.org/0000-0001-6191-1500)
- Alberto López‐Magano (ORCID: https://orcid.org/0000-0001-7980-7218)
- Laura Rodríguez‐Lorenzo (ORCID: https://orcid.org/0000-0002-0315-7981)
- Yury V. Kolen’ko (ORCID: https://orcid.org/0000-0001-7493-1762)
- Manuel Melle‐Franco (ORCID: https://orcid.org/0000-0003-1929-0477)
- Rubén Mas‐Ballesté (ORCID: https://orcid.org/0000-0003-1988-8700)
- Alicia Moya (ORCID: https://orcid.org/0000-0002-0328-012X)
- Mariana Sardo (ORCID: https://orcid.org/0000-0003-3208-4387)
- Karol Strutyński (ORCID: https://orcid.org/0000-0001-8733-9012)
- Clara Ponte (ORCID: https://orcid.org/0000-0003-2929-5730)
- Soraia P. S. Fernandes (ORCID: https://orcid.org/0000-0001-5974-0124)
- Oleg I. Lebedev
- Iñaki Misa
Institutions
- Centre National de la Recherche Scientifique (FR)
- École Nationale Supérieure d'Ingénieurs de Caen (FR)
- Institute for Advanced Medical Research (US)
- Laboratoire de Cristallographie et Sciences des Matériaux (FR)
- International Iberian Nanotechnology Laboratory (PT)
- University of Aveiro (PT)
- Universidade de Vigo (ES)
- Universidad Autónoma de Madrid (ES)
Publication Details
- Journal
- Chemistry of Materials
- Published
- 2025-02-18
- DOI
- https://doi.org/10.1021/acs.chemmater.4c03161
- Citations
- 5
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 2.59
Funders
- European Cooperation in Science and Technology
- Ministerio de Ciencia, Tecnología e Innovación Productiva
- Fundação para a Ciência e a Tecnologia