Substrate and product binding inside a stimuli-responsive coordination cage acting as a singlet oxygen photosensitizer

An acridone-based, interpenetrated double cage [3BF 4 Pd 4 L 8 ] acts as a photosensitizer for generating singlet oxygen which adds to 1,3-cyclohexadiene in a [2+4] hetero-Diels-Alder reaction to form 2,3-dioxabicyclo[2.2.2]oct-5-ene. Photocatalytic activity was exclusively observed for the assemble...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2020-07, Vol.49 (27), p.944-941
Main Authors: Pullen, Sonja, Löffler, Susanne, Platzek, André, Holstein, Julian J, Clever, Guido H
Format: Article
Language:English
Subjects:
Cages
Catalytic activity
Crystallography
Diels-Alder reactions
Ligands
NMR
Nuclear magnetic resonance
Photocatalysis
Self-assembly
Single crystals
Singlet oxygen
Substrates
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Summary:An acridone-based, interpenetrated double cage [3BF 4 Pd 4 L 8 ] acts as a photosensitizer for generating singlet oxygen which adds to 1,3-cyclohexadiene in a [2+4] hetero-Diels-Alder reaction to form 2,3-dioxabicyclo[2.2.2]oct-5-ene. Photocatalytic activity was exclusively observed for the assembled cage, whereas the free organic ligand L decomposes upon irradiation. While cage [3BF 4 Pd 4 L 8 ] does not accept any organic guests, NMR, MS and single crystal X-ray results reveal that both substrate and product are readily encapsulated in the central pocket of its chloride-activated form [2Cl@Pd 4 L 8 ] . The system combines multiple functions (photosensitization, allosteric activation and guest uptake) within a structurally complex, mechanically-bound self-assembly built up from a simple and readily accessible ligand. Multiple functionalities of an acridone-based metallosupramolecular assembly: photosensitization of singlet oxygen, allosteric activation as host and encapsulation of the substrate and product of a hetero-Diels-Alder reaction.
ISSN:1477-9226
1477-9234
DOI:10.1039/d0dt01674h