| Autor: |
Sinelshchikova AA; BCMaterials, Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park, 48940 Leioa, Spain.; Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Building 4, Moscow 119071, Russia., Lapkina LA; Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leniskii pr. 31, Moscow 119991, Russia., Larchenko VE; JSC Fine Chemicals R&D Center, Krasnobogatyrskaya 42, Building 1, Moscow 107258, Russia., Dorovatovskii PV; National Research Center 'Kurchatov Institute', Kurchatov Square 1, Moscow 123182, Russia., Tsivadze AY; Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Building 4, Moscow 119071, Russia.; Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leniskii pr. 31, Moscow 119991, Russia., Gorbunova YG; Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Building 4, Moscow 119071, Russia.; Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leniskii pr. 31, Moscow 119991, Russia. |
| Abstrakt: |
The redox state of the phthalocyanine in sandwich lanthanide complexes is crucial for their applications. In this work, we demonstrate that the cation-induced supramolecular assembly of crown-substituted phthalocyanine lanthanide complexes Ln[(15C5) 4 Pc] 2 can be used to control the redox state of the ligand simultaneously with the coordination sphere of the central metal. We achieve unprecedented redox switching of phthalocyanine ligands in a double-decker Gd(III) complex, resulting from the intramolecular inclusion of potassium cations between the decks with simultaneous twisting of the ligands (the skew angle between them decreases from 44.61 to 0.21°). Such a structural change leads to an increase in the deck-to-deck distance and drastically facilitates ligand reduction. This process was shown to be anion-dependent: only potassium salts of weak acids (KOPiv and KOAc) induce intramolecular inclusion of cations with redox switching in contrast to salts of strong acids (KBr, KOPic, KSCN, and KPF 6 ), where such a redox process does not occur. This breakthrough opens new avenues for controlling the electrochromic properties, of phthalocyanines, along with other properties, such as electrical conductivity, optics, etc. |
