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Taming a silent killer : uncovering the role of excited states and uncoordinated selenium moieties in the CO photorelease mechanism of manganese(i) carbonyl compounds

Glitz, Vinícius LU orcid ; Durigon, Daniele Cocco LU orcid ; Amorim, André Luiz LU ; Ricken, Yara Schuvinski ; Bortoluzzi, Adailton João ; Braga, Antonio Luiz ; Nordlander, Ebbe LU ; Caramori, Giovanni Finoto and Peralta, Rosely Aparecida (2025) In Inorganic Chemistry Frontiers 12(15). p.4677-4690
Abstract

Manganese carbonyl compounds can release CO when exposed to light, potentially becoming photochemically activated CO-releasing molecules (photoCORMs). Several studies have demonstrated the behavior in the ground state when irradiated with light. However, much remains to be discovered about the chemistry of photoCORMs with uncoordinated ligand moieties and the excited states of these compounds. This research fills that gap via the synthesis, characterization, and study of the excited states of five manganese(i) complexes containing a potentially bi- or tridentate ligand framework (κn-Se,N,Se; n = 2, 3). The obtained compounds, [Mn(κ2-L)(CO)3Br], retain a uncoordinated selenium-donor moiety. CO-release... (More)

Manganese carbonyl compounds can release CO when exposed to light, potentially becoming photochemically activated CO-releasing molecules (photoCORMs). Several studies have demonstrated the behavior in the ground state when irradiated with light. However, much remains to be discovered about the chemistry of photoCORMs with uncoordinated ligand moieties and the excited states of these compounds. This research fills that gap via the synthesis, characterization, and study of the excited states of five manganese(i) complexes containing a potentially bi- or tridentate ligand framework (κn-Se,N,Se; n = 2, 3). The obtained compounds, [Mn(κ2-L)(CO)3Br], retain a uncoordinated selenium-donor moiety. CO-release assays using violet light revealed the formation of a biscarbonyl intermediate. TD-DFT calculations showed that in [Mn(κ2-L)(CO)3Br], the first two excited states are involved. Generalized Kohn-Sham energy decomposition analysis indicated that the strongest metal-carbonyl interaction in the ground state (carbonyl trans to bromide) became the weakest in the excited state. DFT calculations confirmed the coordination of free selenium upon CO loss, forming [Mn(κ3-L)(CO)2Br], for which two configurational isomers (meridional and facial) may occur, with the first being more favored. The total interaction energies of the two carbonyls are similar, indicating the release of both. The potential energy curves indicate that the excited states involved are dissociative in nature.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry Frontiers
volume
12
issue
15
pages
14 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:105003037526
ISSN
2052-1553
DOI
10.1039/d5qi00162e
language
English
LU publication?
yes
id
8b493ade-d9c7-4648-9688-f691378c3348
date added to LUP
2025-08-29 12:49:59
date last changed
2025-08-29 12:49:59
@article{8b493ade-d9c7-4648-9688-f691378c3348,
  abstract     = {{<p>Manganese carbonyl compounds can release CO when exposed to light, potentially becoming photochemically activated CO-releasing molecules (photoCORMs). Several studies have demonstrated the behavior in the ground state when irradiated with light. However, much remains to be discovered about the chemistry of photoCORMs with uncoordinated ligand moieties and the excited states of these compounds. This research fills that gap via the synthesis, characterization, and study of the excited states of five manganese(i) complexes containing a potentially bi- or tridentate ligand framework (κ<sup>n</sup>-Se,N,Se; n = 2, 3). The obtained compounds, [Mn(κ<sup>2</sup>-L)(CO)<sub>3</sub>Br], retain a uncoordinated selenium-donor moiety. CO-release assays using violet light revealed the formation of a biscarbonyl intermediate. TD-DFT calculations showed that in [Mn(κ<sup>2</sup>-L)(CO)<sub>3</sub>Br], the first two excited states are involved. Generalized Kohn-Sham energy decomposition analysis indicated that the strongest metal-carbonyl interaction in the ground state (carbonyl trans to bromide) became the weakest in the excited state. DFT calculations confirmed the coordination of free selenium upon CO loss, forming [Mn(κ<sup>3</sup>-L)(CO)<sub>2</sub>Br], for which two configurational isomers (meridional and facial) may occur, with the first being more favored. The total interaction energies of the two carbonyls are similar, indicating the release of both. The potential energy curves indicate that the excited states involved are dissociative in nature.</p>}},
  author       = {{Glitz, Vinícius and Durigon, Daniele Cocco and Amorim, André Luiz and Ricken, Yara Schuvinski and Bortoluzzi, Adailton João and Braga, Antonio Luiz and Nordlander, Ebbe and Caramori, Giovanni Finoto and Peralta, Rosely Aparecida}},
  issn         = {{2052-1553}},
  language     = {{eng}},
  number       = {{15}},
  pages        = {{4677--4690}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Inorganic Chemistry Frontiers}},
  title        = {{Taming a silent killer : uncovering the role of excited states and uncoordinated selenium moieties in the CO photorelease mechanism of manganese(i) carbonyl compounds}},
  url          = {{http://dx.doi.org/10.1039/d5qi00162e}},
  doi          = {{10.1039/d5qi00162e}},
  volume       = {{12}},
  year         = {{2025}},
}