Tuning of the photophysical and electrochemical properties of ruthenium(II) phthalocyaninates by variation of axial ligands

Dmitrienko, A.A.; Kroitor, A.P.; Bunin, D.A.; Arakcheev, A.V.; Martynov, A.G.; Selektor, S.L.; Tsivadze, A.Y.; Gorbunova, Y.G.

Авторы: Dmitrienko Alexander A., Kroitor Andrey P., Bunin Dmitry A., Arakcheev Andrey V., Martynov Alexander G., Selektor Sofiya L., Tsivadze Aslan Yu, Gorbunova Yulia G.
Журнал: Journal of Coordination Chemistry
Том: 77
Номер: 11
Год издания: 2024
Издательство: Gordon and Breach Science Publishers
Местоположение издательства: Switzerland
Первая страница: 1220
Последняя страница: 1235
DOI: 10.1080/00958972.2024.2352485
Аннотация: ABSTRACT A series of mononuclear ruthenium(II) tetra-tert-butyl-phthalocya- ninates bearing axial N-donor ligands [tBu4PcRu]L2 (L¼ trimethylamine, pyrazine, 4,40-bipyridine and N-methyl-4,40- bipyridinium iodide) as well as the binuclear complex [tBu4PcRu]2(BiPy)3 were synthesized starting from the complex with axially coordinated carbonyl group [tBu4PcRu](CO). All com- pounds have been characterized by NMR, UV-Vis and cyclic vol- tammetry. The latter allowed the determination of oxidation and reduction potentials, HOMO-LUMO gaps and revealed the possi- bility of electropolymerization of BiPy-containing complexes in clear contrast to complexes containing another bidentate ligand – pyrazine. Comparative electrochemical studies of the mono- and binuclear complexes [tBu4PcRu](BiPy)2 and [tBu4PcRu]2(BiPy)3 revealed that the phthalocyanine rings are not conjugated in the binuclear species. The remarkable dependence of singlet oxygen generation from axial ligands in ruthenium phthalocyaninates was observed; the complexes with carbonyl group [tBu4PcRu](CO) and with pyrazine molecules [tBu4PcRu](Pyz)2 show higher 1O2 quan- tum yields, whereas the complex with axially coordinated mole- cules of trimethylamine [tBu4PcRu](NMe3)2 and quaternized BiPy ligands [tBu4PcRu](BiPy-Meþ)2 have the lowest ability to generate singlet oxygen. The revealed influence of axial ligands on key physicochemical properties paves the way for the design of new ruthenium phthalocyaninates with potential optoelectronic and biomedical applications
Добавил в систему: Кройтор Андрей Петрович

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