Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction

Philip M Stanley; Johanna Haimerl; Christopher Thomas; Alexander Urstoeger; Michael Schuster; Natalia B Shustova; Angela Casini; Bernhard Rieger; Julien Warnan; Roland A Fischer

doi:10.1002/anie.202102729

Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO₂ Reduction

Angew Chem Int Ed Engl. 2021 Aug 9;60(33):17854-17860. doi: 10.1002/anie.202102729. Epub 2021 Jun 1.

Authors

Affiliations

¹ Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, Garching, Germany.
² WACKER-Chair of Macromolecular Chemistry, Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, Garching, Germany.
³ Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina, USA.
⁴ Division of Analytical Chemistry, Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, Garching, Germany.
⁵ Chair of Medicinal and Bioinorganic Chemistry, Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, Garching, Germany.

Abstract

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO₂ reduction catalyst [ReBr(CO)₃ (4,4'-dcbpy)] and a photosensitizer [Ru(bpy)₂ (5,5'-dcbpy)]Cl₂ using the isoreticular series of metal-organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location-either at the outer MOF particle surface or inside the MOF cavities-affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.

Keywords: host-guest systems; hybrid materials; metal-organic frameworks; molecular catalysis; solar fuel production.

Abstract

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