Direct observation of photoinduced bent nitrosyl excited-state complexes

The Journal of Physical Chemistry. a
Karma R SawyerCharles B Harris

Abstract

Ground-state structures with side-on nitrosyl (eta (2)-NO) and isonitrosyl (ON) ligands have been observed in a variety of transition-metal complexes. In contrast, excited-state structures with bent-NO ligands have been proposed for years but never directly observed. Here, we use picosecond time-resolved infrared spectroscopy and density functional theory (DFT) modeling to study the photochemistry of Co(CO) 3(NO), a model transition-metal-NO compound. Surprisingly, we have observed no evidence for ON and eta (2)-NO structural isomers, but we have observed two bent-NO complexes. DFT modeling of the ground- and excited-state potentials indicates that the bent-NO complexes correspond to triplet excited states. Photolysis of Co(CO) 3(NO) with a 400-nm pump pulse leads to population of a manifold of excited states which decay to form an excited-state triplet bent-NO complex within 1 ps. This structure relaxes to the ground triplet state in ca. 350 ps to form a second bent-NO structure.

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Citations

Jun 21, 2013·Physical Chemistry Chemical Physics : PCCP·Konstantin E DorfmanShaul Mukamel
Jan 27, 2010·Journal of the American Chemical Society·Karma R SawyerCharles B Harris
Dec 16, 2020·The Journal of Physical Chemistry. a·Hiroyuki NakataHiroshi Kohguchi
Jan 7, 2022·Dalton Transactions : an International Journal of Inorganic Chemistry·G Grieco, O Blacque

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