Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Nazarov, D.I.; Islyaikin, M.K.; Ivanov, E.N.; Koifman, O.I.; Batov, M.S.; Zorina, L.V.; Khasanov, S.S.; Shestakov, A.F.; Yudanova, E.I.; Zhabanov, Y.A.; Vyalkin, D.A.; Otsuka, A.; Yamochi, H.; Kitagawa, H.; Torres, T.; Konarev, D.V.

Авторы: Nazarov Dmitry I., Islyaikin Mikhail K., Ivanov Evgenii N., Koifman Oskar I., Batov Mikhail S., Zorina Leokadiya V., Khasanov Salavat S., Shestakov Alexander F., Yudanova Evgeniya I., Zhabanov Yuriy A., Vyalkin Dmitriy A., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Torres Tomas, Konarev Dmitri V.
Журнал: Inorganic Chemistry
Том: 60
Номер: 13
Год издания: 2021
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 9857
Последняя страница: 9868
DOI: 10.1021/acs.inorgchem.1c01132
Аннотация: Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain MII3O clusters inside a π-extended trianionic (Hhp3–) macrocycle have been prepared. Studies of the magnetic properties of NiII3O(Hhp) and CuII3O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp3–) macrocycle and diamagnetic NiII3(O2–) or paramagnetic CuII3(O2–) tetracations. The positive charge of MII3O(Hhp) is compensated by one acetate anion {MII3O(Hhp)}+(CH3CO2–). The three-electron reduction of {MII3O(Hhp)}+ yields {cryptand(Cs+)}2{NiII2NiIO(Hhp5–)}2–·2C7H8 (1) and {cryptand(Cs+)}2{CuII3O(Hhp•6–)}2–·C7H8 (2) crystalline salts. The magnetic properties of 1 reveal the formation of Hhp(5–) and the reduction of nickel(II) to the paramagnetic NiI ion (S = 1/2), which is accompanied by the formation of the {NiII2NiIO(Hhp5–)}2– dianion. As a result, the magnetic moment of 1 is 1.68 μB in the 20–220 K range, and a broad EPR signal of NiI was observed. The Hhp5– macrocycle has a singlet ground state, but the increase in the magnitude of the magnetic moment of 1 above 220 K is attributed to the population of the triplet excited state in Hhp(5–). The {NiII2NiIO(Hhp5–)}2– dianion is transferred from the doublet excited state to the quartet excited state with an energy gap of 1420 ± 50 K. Salt 1 also shows an unusually strong low-energy NIR absorption, which was observed at 1000–2200 nm. In 2, a highly reduced Hhp(•6–) radical hexaanione (S = 1/2) coexists with a CuII3(O2–) cluster (S = 1/2) in the {CuII3O(Hhp•6–)}2– dianions. The dianions have a triplet ground state with antiferromagnetic exchange between two S = 1/2 spins with J = −6.4 cm–1. The reduction of Hhp in both salts equalizes the initially alternated C–N bonds, supporting the increase in the Hhp macrocycle electron delocalization.
Добавил в систему: Батов Михаил Сергеевич

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Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianionsстатья