Wavelength-selective photoisomerisation of nitric oxide and nitrite in a rhodium complex

Abstract

Photoinduced linkage isomers (PLIs) of NO and NO2− are selectively generated by an appropriate choice of irradiation wavelength at low temperature within the same molecular complex [Rh(NO)(NO2)2(But2PH)2].

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

“…31 Such nitro-nitrosyl ruthenium complexes were also used as anions with tetranuclear ruthenium lanthanide complexes in order to combine the PLI with single molecular magnets, 113 even though the potential interplay between the magnetic and photoswitchable properties was not reported. Nitro-nitrosyl complexes offer in principle the possibility to observe both linkage isomers of the NO and the NO 2 ligand, 140,141 and thus a multitude of PLI combinations that might be useful for applications. A non-centrosymmetric structure of such a nitro-nitrosyl ruthenium complex with 3-cyanopyridine ligand was reported, but only nitrosyl isomers could be observed and the effect of this PLI generation on the nonlinear optical properties was not reported.…”

Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes

“…Initial model-independent evidence for NO isomerization is obtained by analysis of photodifference maps, an adequate tool for the study of structural changes even in the case of low populations (Schaniel et al, 2018). The same single crystal used for the GS structure determination was used for MS1 data collection after irradiation at 405 nm (360 mW LED for 120 min).…”

“…Note that the F-Ru-N-O axis is almost perpendicular to the b axis, so the small increase in a and c might be expected from the lengthening of the Ru-O distance in the Ru-ON (MS1) bond compared with the Ru-N distance in Ru-NO (GS). The photodifference map is the Fourier transform of the difference between the structure factors of the photoexcited structure (GS+MS1) and the structure before irradiation (GS) (Schaniel et al, 2018). For the present case, the photodifference map (Fig.…”