Studying manganese carbonyl photochemistry in a permanently porous metal–organic framework

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dc.contributor.authorYoung, R.J.
dc.contributor.authorHuxley, M.T.
dc.contributor.authorWu, L.
dc.contributor.authorHart, J.
dc.contributor.authorO'Shea, J.
dc.contributor.authorDoonan, C.J.
dc.contributor.authorChampness, N.R.
dc.contributor.authorSumby, C.J.
dc.date.issued2023
dc.descriptionFirst published 15 Aug 2023
dc.description.abstractMn(diimine)(CO)₃X (X = halide) complexes are critical components of chromophores, photo- and electrocatalysts, and photoactive CO-releasing molecules (photoCORMs). While these entities have been incorporated into metal–organic frameworks (MOFs), a detailed understanding of the photochemical and chemical processes that occur in a permanently porous support is lacking. Here we site-isolate and study the photochemistry of a Mn(diimine)(CO)₃Br moiety anchored within a permanently porous MOF support, allowing for not only the photo-liberation of CO from the metal but also its escape from the MOF crystals. In addition, the high crystallinity and structural flexibility of the MOF allows crystallographic snapshots of the photolysis products to be obtained. We report these photo-crystallographic studies in the presence of coordinating solvents, THF and acetonitrile, showing the changing coordination environment of the Mn species as CO loss proceeds. Using time resolved experiments, we report complementary spectroscopic studies of the photolysis chemistry and characterize the final photolysis product as a possible Mn(II) entity. These studies inform the chemistry that occurs in MOF-based photoCORMs and where these moieties are employed as catalysts.
dc.description.statementofresponsibilityRosemary J. Young, Michael T. Huxley, Lingjun Wu, Jack Hart, James O'Shea, Christian J. Doonan, Neil R. Champness and Christopher J. Sumby
dc.identifier.citationChemical Science, 2023; 14(35):9409-9417
dc.identifier.doi10.1039/d3sc03553k
dc.identifier.issn2041-6520
dc.identifier.issn2041-6539
dc.identifier.orcidSumby, C.J. [0000-0002-9713-9599]
dc.identifier.urihttps://hdl.handle.net/2440/139441
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.relation.granthttp://purl.org/au-research/grants/arc/DP190101402
dc.rights© 2023 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
dc.source.urihttps://doi.org/10.1039/d3sc03553k
dc.titleStudying manganese carbonyl photochemistry in a permanently porous metal–organic framework
dc.typeJournal article
pubs.publication-statusPublished

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