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    Spin Crossover in Nickel(II) Tetraphenylporphyrinate via Forced Axial Coordination at the Air/Water Interface

    Year: 2021

    Journal: Molecules, Volume 26, JUL

    Authors: Shokurov, Alexander V.; Kutsybala, Daria S.; Kroitor, Andrey P.; Dmitrienko, Alexander A.; Martynov, Alexander G.; Enakieva, Yulia Yu.; Tsivadze, Aslan Yu.; Selektor, Sofiya L.; Gorbunova, Yulia G.

    Organizations: Ministry of Science and Higher Education of Russia [075-15-2020-782]

    Keywords: nickel porphyrinate; spin crossover; ruthenium phthalocyaninate; supramolecular; axial coordination; air; water interface; Langmuir monolayer; optical response

    Coordination-induced spin crossover (CISCO) in nickel(II) porphyrinates is an intriguing phenomenon that is interesting from both fundamental and practical standpoints. However, in most cases, realization of this effect requires extensive synthetic protocols or extreme concentrations of extra-ligands. Herein we show that CISCO effect can be prompted for the commonly available nickel(II) tetraphenylporphyrinate, NiTPP, upon deposition of this complex at the air/water interface together with a ruthenium(II) phthalocyaninate, CRPcRu(pyz)(2), bearing two axial pyrazine ligands. The latter was used as a molecular guiderail to align Ni center dot center dot center dot Ru center dot center dot center dot Ni metal centers for pyrazine coordination upon lateral compression of the system, which helps bring the two macrocycles closer together and forces the formation of Ni-pyz bonds. The fact of Ni(II) porphyrinate switching from low- to high-spin state upon acquiring additional ligands can be conveniently observed in situ via reflection-absorption UV-vis spectroscopy. The reversible nature of this interaction allows for dissociation of Ni-pyz bonds, and thus, change of nickel cation spin state, upon expansion of the monolayer.
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