Unravelling the Atomic Structure of a Metal‐Covalent Organic Framework Assembled from Ruthenium Metalloligands
Covalent and metal-organic frameworks (COFs and MOFs) have shown great promise in light-driven processes mainly due to their ligand-to-metal charge-separation properties, as well as having access to a diverse range of photoactive metalloligands and organic linkers. However, both frameworks present individual drawbacks that can potentially be avoided by combining both systems (metal and covalent) to produce metal-covalent organic frameworks (MCOFs), exhibiting the advantages of both material types. Yet, due to their poor crystallinity, the understanding of the structure-properties relation of MCOFs remains unclear. Herein, we report photoactive linkers in the form of a [Ru(tpy)<sub>2</sub>]<sup>2+</sup> (tpy: 2,2',6,2″-terpyridine) complex which covalently binds to a luminescent pyrene core to yield a new, photoactive Schiff-base MCOF. The structure, thermal, electronic, and optical properties of this novel material have been exhaustively characterized by a wide range of microscopy, spectroscopic, and computational methods. This combined experimental and computational work represents a significant step toward the fundamental understanding of the photoactive units within the framework, their hierarchical arrangement and interactions with substrates, which is essential for the future design of efficient photocatalytic materials.
Authors
- Michael John Zaworotko (ORCID: https://orcid.org/0000-0002-1360-540X)
- Kunal S. Mali (ORCID: https://orcid.org/0000-0002-9938-6446)
- Seán Hennessey (ORCID: https://orcid.org/0000-0002-5406-518X)
- Andrey A. Bezrukov (ORCID: https://orcid.org/0000-0002-0525-3547)
- Nadezda V. Tarakina (ORCID: https://orcid.org/0000-0002-2365-861X)
- Max García‐Melchor (ORCID: https://orcid.org/0000-0003-1348-4692)
- Nicolás Arisnabarreta (ORCID: https://orcid.org/0000-0002-9546-1250)
- Anna Ciotti
- Pau Farràs (ORCID: https://orcid.org/0000-0003-3859-2868)
- Steven De Feyter (ORCID: https://orcid.org/0000-0002-0909-9292)
- Jing Hou (ORCID: https://orcid.org/0000-0001-5542-4175)
- Roberto González‐Gómez (ORCID: https://orcid.org/0000-0003-4200-2541)
Institutions
- Ikerbasque (ES)
- Ollscoil na Gaillimhe – University of Galway (IE)
- Trinity College Dublin (IE)
- University of Limerick (IE)
- Max Planck Institute of Colloids and Interfaces (DE)
- Advanced Materials and BioEngineering Research (IE)
- CIC energiGUNE (ES)
- KU Leuven (BE)
Publication Details
- Journal
- Advanced Materials
- Published
- 2025-02-19
- DOI
- https://doi.org/10.1002/adma.202502155
- Citations
- 8
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 4.14
Funders
- European Commission
- Science Foundation Ireland
- University of Galway
- Fonds Wetenschappelijk Onderzoek
- KU Leuven
- King Abdullah University of Science and Technology
- Max-Planck-Gesellschaft
- Vlaamse regering
- Irish Centre for High-End Computing
- Horizon 2020 Framework Programme
- HORIZON EUROPE Framework Programme
- H2020 Excellent Science