Details

Autor(en) / Beteiligte

• Gansmüller, Axel
• Mikhailov, Artem A
• Kostin, Gennadiy A
• Raya, Jésus
• Palin, Cyril
• Woike, Theo
• Schaniel, Dominik

Titel

Solid-State Photo-NMR Study on Light-Induced Nitrosyl Linkage Isomers Uncovers Their Structural, Electronic, and Diamagnetic Nature

Ist Teil von

• Analytical chemistry (Washington), 2022-03, Vol.94 (10), p.4474-4483

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2022

Quelle

MEDLINE

Beschreibungen/Notizen

• A light-induced linkage NO isomer (MS1) in trans-[Ru­(15NO)­(py)4 19F]­(ClO4)2 is detected and measured for the first time by solid-state MAS NMR. Chemical shift tensors of 15N and 19F, along with n J(15N–19F) spin–spin couplings and T 1 relaxation times of MS1, are compared with the ground state (GS) at temperatures T < 250 K. Isotropic chemical shifts (15N and 19F) are well resolved for two crystallographically independent cations (A and B) [Ru­(15NO)­(py)4 19F]2+, allowing to define separately both populations of MS1 isomers and thermal decay rates for two structural sites. The relaxation times T 1 of 19F in the case of GS (30/38.6 s for sites A/B) and MS1 (11.6/11.8 s for sites A/B) indicate that both isomers are diamagnetic, which is the first experimental evidence of diamagnetic properties of MS1 in ruthenium nitrosyl. After light irradiation (λ = 420 nm), the NO ligand rotates by nearly 180° from F–Ru–N–O to F–Ru–O–N, whereby the isotropic chemical shifts of δiso(15N) increase and those of δiso(19F) decrease. The n J(15N–19F) couplings increase from 2 J(15N–Ru–19F)GS = 71 Hz to 3 J(15N–O–Ru–19F)MS1 = 105 Hz. These results are interpreted on the basis of DFT–CASTEP calculations including Bader-, Mulliken-, and Hirshfeld-charge density distributions of both states.