Spin Crossover in Nickel(II) Tetraphenylporphyrinate via Forced Axial Coordination at the Air/Water Interface
Autor: | Sofiya L. Selektor, Andrey P. Kroitor, Yulia G. Gorbunova, Alexander A. Dmitrienko, Alexander V. Shokurov, Yulia Yu. Enakieva, Aslan Yu. Tsivadze, Alexander G. Martynov, Daria S. Kutsybala |
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Jazyk: | angličtina |
Rok vydání: | 2021 |
Předmět: |
Materials science
Pyrazine Spin states Supramolecular chemistry Pharmaceutical Science chemistry.chemical_element Organic chemistry ruthenium phthalocyaninate 010402 general chemistry 01 natural sciences Article Dissociation (chemistry) Analytical Chemistry chemistry.chemical_compound QD241-441 spin crossover Spin crossover Drug Discovery Monolayer Langmuir monolayer Physical and Theoretical Chemistry optical response 010405 organic chemistry air/water interface 0104 chemical sciences Ruthenium Crystallography Nickel chemistry Chemistry (miscellaneous) Molecular Medicine axial coordination nickel porphyrinate supramolecular |
Zdroj: | Molecules, Vol 26, Iss 4155, p 4155 (2021) Molecules Volume 26 Issue 14 |
ISSN: | 1420-3049 |
Popis: | 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···Ru···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. |
Databáze: | OpenAIRE |
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