Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers

• Published in: Angewandte Chemie International Edition Vol. 62; no. 44; p. e202310878
• Main Authors: Jabbour, Ribal, Ashling, Christopher W., Robinson, Thomas C., Khan, Arafat Hossain, Wisser, Dorothea, Berruyer, Pierrick, Ghosh, Ashta C., Ranscht, Alisa, Keen, David A., Brunner, Eike, Canivet, Jérôme, Bennett, Thomas D., Mellot‐Draznieks, Caroline, Lesage, Anne, Wisser, Florian M.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 26-10-2023; Wiley-VCH Verlag
• Edition: International ed. in English
• Subjects: Amorphous materials; Atomic structure; Catalysis; Catalysts; Catalytic activity; Chemical Sciences; Computational chemistry; Confining; Coordination compounds; Distribution functions; Environment and Society; Environmental Sciences; Function analysis; Magnetic resonance spectroscopy; Metal complexes; Molecular structure; NMR; NMR spectroscopy; Nuclear magnetic resonance; Polymers; Xenon 129
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202310878

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic‐level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non‐crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis,
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Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh‐based organometallic complex incorporated inside the cavity of amorphous bipyridine‐based porous polymers is obtained. Small, but significant, differences in the structural properties of the polymers are highlighted depending on their backbone motifs.