High thermal stability of the Ru–ON (MS1) linkage isomer of the ruthenium nitrosyl complex [RuNO(Py)₄F](ClO₄)₂ with the trans NO–Ru–F coordinate

Abstract

The [RuNO(Py)4F](ClO4)2 complex with the highest thermal stability of the Ru–ON linkage isomer.

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

“…The increase of the available volume per nitrosyl group is 0.567 Å 3 being slightly larger than the free volume around single nitrosyl group. Compound 1 has the smallest available volume for the nitrosyl group compare to the trans ‐[RuNOPy 4 F](ClO 4 ) 2 (0.9–1.4 Å 3 ) and cis ‐[RuNO(NH 3 ) 2 (NO 2 ) 2 OH] (1.0–1.5 Å 3 ) . This fact could cause hindrance of NO rotation from the photogenerated O ‐coordinated isomer to the ground state with N ‐bound nitrosyl.…”

“…The cavity analysis was a 1.2 Å test atom walk through a (10,10,5) Å box around the nitrosyl group with 0.01 Å steps. This method is similar to the study of cobaltoxime complexes and was implemented for other ruthenium nitrosyl complexes , . The ruthenium radius equal to the difference between the Ru–NO bond length and the test atom radius.…”

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

“…3). The (ON) band of MS1 exhibits a shift of 133 cm À1 to lower energy compared with the (NO) band of GS, which is typical for ruthenium nitrosyl compounds (Schaniel, Cormary et al, 2007;Kostin et al, 2015Kostin et al, , 2017Kostin et al, , 2018. The most efficient wavelengths for inducing the GS-to-MS1 transfer are in the range 405-420 nm (Fig.…”

“…The synthesis of trans-[RuNO(NH 3 ) 4 F] 2+ was performed in an analogous manner to that of the trans-[RuNO(py) 4 F] 2+ complex from our previous work (Kostin et al, 2018). trans-[RuNO(NH 3 ) 4 OH]Cl 2 (585 mg) was dissolved in concentrated HF (10 ml, 40%) and heated in a closed polypropylene vessel for 30 h at 363 K. The solution was then evaporated in air to dryness, resulting in a yellow residue.…”

“…In previous work we have shown that [RuNO-(py) 4 F](ClO 4 ) 2 exhibits the highest MS1 thermal stability and that MS1 can be photogenerated by blue light up to 230 K using a continuous-wave (CW) light source for irradiation, and even at room temperature when using pulsed laser irradiation (Kostin et al, 2018;Mikhailov et al, 2019). We also showed that the thermal stability of MS2 is essential for the roomtemperature generation of MS1, as the GS to MS1 excitation occurs via MS2 as an intermediate state (Mikhailov et al, 2019).…”