Abstract: Both ruthenium nitrosyls and nitroxide radicals are of interest due to their unique biological properties and versatile solid-state chemistry. Thus, the combination of organic and inorganic NO moieties in one complex can results in the properties synergy. Still the synthetic pathways for preparation of RuNO and nitroxide radicals usually requires conflicting conditions and combination of these fragments is not the simple way. We proposed the synthetic approach to the preparation of Na[RuNOCl4L] (see Fig.) and investigated its photochemical and magnetic properties. The crystal structure of synthetized complexes consists from polymeric chains containing [RuNOCl4L]- anions bonded by sodium cations coordinated by NO nitroxide group. According to ESI-MS similar oligomers are also detected in the acetonitrile solutions. High temperature magnetic moments of all three complexes with different nitroxides well correspond to the S = ½ the decrease of temperature results in the magnetic interactions in the chains. Blue light irradiation of complex acetonitrile solutions results in the three-stage process including the cleavage of Ru-NO bond with the formation of free nitric oxide, the interaction of NO with nitroxide radicals and finally the back formation of Ru-NO.

Cite: Kostin G. , Bogomyakov A. , Tolstikov S.
Ruthenium nitrosyl complexes with substituted nitronyl-nitroxides.
HIGH-SPIN MOLECULES AND MOLECULAR MAGNETS 09-14 Jul 2023