Evidence for a photoinduced isonitrosyl isomer in ruthenium dinitrosyl compounds

Abstract

Photo-induced NO rotation from N-bound (blue) to O-bound (red) with blue light at 100 K in the compound [Ru(NO)2(PCy3)2Cl]BF4.

Exploring Photoswitchable Properties of Two Nitro Nickel(II) Complexes with (N,N,O)-Donor Ligands and Their Copper(II) Analogues

“…Molecular switches triggered by UV–vis light may find wide applications in high-capacity storage devices, optoelectronics, medicine, as color-changing materials, etc. , Therefore, the importance of studies dedicated to the conscious design of new functional photoswitchable systems with the desired properties cannot be overestimated. − Transition-metal complexes in which the metal center is coordinated by molecular fragments that can exist in multiple isomeric forms are among the potential functional materials of this kind . Examples of ambidentate ligands known to display solid-state linkage isomerism include NO, , NO 2 , ,,− SO 2 , − SCN, and N 2. Transition-metal complexes containing nickel, ,,, cobalt, − iron, ruthenium, , osmium, palladium, or platinum − , centers are the most representative examples of such systems.…”

Photocrystallographic and spectroscopic studies of a model (N,N,O)-donor square-planar nickel(II) nitro complex: in search of high-conversion and stable photoswitchable materials

“…Photoswitchable transitionmetal complexes, in which the metal centre (e.g. Ni, Co, Pd, Rh) is coordinated by ambidentate ligands, such as NO, NO 2 or SO 2 moieties, are the most representative examples of such systems (Kovalevsky et al, 2005;Hatcher et al, 2011Cole et al, 2018;Sylvester et al, 2014;Bowes et al, 2006;Schaniel et al, 2019Schaniel et al, , 2018Schaniel, Nicoul & Woike, 2010;Cormary et al, 2012;Coppens et al, 2002). Under certain conditions they can be switched from the ground-state form to a metastable linkage isomer by light of a suitable wavelength, which may further influence their macroscopic properties, e.g.…”

Ruthenium-nitrosyl complexes as NO-releasing molecules, potential anticancer drugs, and photoswitches based on linkage isomerism

“…By choosing an appropriate irradiation wavelength and temperature, the PLI-2 in one of the complexes could be isolated and its structural configuration was investigated by photocrystallography. 145 The results point in this case to an iso-nitrosyl configuration, i.e. Ru-O-N, exhibiting ∠Ru-O-N = 125°, close to ∠Ru-N-O = 136°found in the GS.…”

“…14 Scheme illustrating the photogeneration of nitrosyl linkage isomers in RuCl(NO) 2 (PCy 3 ) 2 BF 4 according to results reported recently. 80,145 By using different irradiation wavelengths and adjusting the temperature the complex can selectively undergo either PLI-1 or PLI-2, e.g. irradiation with 405 nm in the temperature range 70-130 K results in PLI-2 (right branch) while irradiation with 405 nm below 60 K followed by irradiation with 980 nm results in PLI-1 (left branch, through depopulation of PLI-2 by 980 nm irradiation).…”