Unravelling the Atomic Structure of a Metal-Covalent Organic Framework Assembled from Ruthenium Metalloligands.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39972930.
- Also identified by DOI 10.1002/adma.202502155 and PMC identifier 11962698.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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.