Easy access to powerful ruthenium phthalocyanine high-oxidized species

Ruthenium(III) phthalocyanine was synthesized using the solvent assisted approach from RuCl3 center dot nH(2)O first compound with chlorinated solvents was observed to result in generation of stable pi-cation radical (RuPc+center dot)-Pc-II, which was capable of oxidizing beta-carotene. The spectral properties UV-visible, IR, EPR as well as electrochemical properties of the complexes were examined. The structure of the compound was supported by MALDI TOF and DFT calculations. The reaction of the one-oxidized species with tBuOOH and H2O2, afforded chemical generation of doubly oxidized species (RuPc2+)-Pc-II and (RuPc+center dot)-Pc-III, respectively, which were stable for several hours and were detected spectrally. All the high-charge compounds under study were found to be catalytically active in the oxidative degradation of beta-carotene. The reaction was examined in dichloromethane at ambient temperature under visible light. The results showed that the dication species (RuPc2+)-Pc-II is the most powerful oxidant and facilitates the immediate beta-carotene oxidation followed by destruction of the intermediate products. The (RuPc+center dot)-Pc-II species turned out to be more durable, recoverable and stable under the reaction conditions. After complete beta-carotene decay, the active species could readily be regenerated under the conditions of the reaction medium allowing catalytic cycle upon substrate addition. The experimentally assessed characteristics were also correlated with the electronic structure predicted by DFT analyses. As viable candidate species for catalytic systems based on ruthenium phthalocyanines, these highly charged species hold great promise for oxidation via activating oxidant, which could ensure their effective using.