Issue 35, 2023

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

Abstract

Mn(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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Jūl. 2023
Accepted
14 Aug. 2023
First published
15 Aug. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 9409-9417

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

R. J. Young, M. T. Huxley, L. Wu, J. Hart, J. O'Shea, C. J. Doonan, N. R. Champness and C. J. Sumby, Chem. Sci., 2023, 14, 9409 DOI: 10.1039/D3SC03553K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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