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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

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

Author

  • Vinícius Glitz
  • Daniele Cocco Durigon
  • André Luiz Amorim
  • Yara Schuvinski Ricken
  • Adailton João Bortoluzzi
  • Antonio Luiz Braga
  • Ebbe Nordlander
  • Giovanni Finoto Caramori
  • Rosely Aparecida Peralta

Summary, in English

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.

Department/s

  • Chemical Physics
  • LU Profile Area: Light and Materials

Publishing year

2025-07

Language

English

Pages

4677-4690

Publication/Series

Inorganic Chemistry Frontiers

Volume

12

Issue

15

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Theoretical Chemistry (including Computational Chemistry)

Status

Published

ISBN/ISSN/Other

  • ISSN: 2052-1553