Journal
INORGANIC CHEMISTRY
Volume 54, Issue 12, Pages 5827-5838Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b00546
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Funding
- Russian Science Foundation [14-13-00724]
- Council of the President of the Russian Federation [MD-3589.2014.3]
- Russian Academy of Sciences [5]
- Russian Science Foundation [14-13-00724] Funding Source: Russian Science Foundation
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Template condensation of dichloroglyoxime with n-hexadecylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded n hexadecylboron-capped iron and cobalt(II) hexachloroclathrochelates. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV vis, H-1 and C-13{1H} NMR, Fe-57 Mossbauer spectroscopies, SQUID magnetometry, electron paramagnetic resonance, and cyclic voltammetry (CV) and by X-ray crystallography. The multitemperature single-crystal X-ray diffraction, SQUID magnetometry, and differential scanning calorimetry experiments were performed to study the temperature-induced spincrossover [for the paramagnetic cobalt(II) complex] and the crystal-to-crystal phase transitions (for both of these dathrochelates) in the solid state. Analysis of their crystal packing using the molecular Voronoi polyhedra and the Hirshfeld surfaces reveals the structural rearrangements of the apical long-chain alkyl substituents resulting from such phase transitions being more pronounced for a macrobicyclic cobalt(II) complex. Its fine-crystalline sample undergoes the gradual and fully reversible spin transition centered at approximately 225 K. The density functional theory calculated parameters for an isolated molecule of this cobalt(II) hexachloroclathrochelate in its low- and high-spin states were found to be in excellent agreement with the experimental data and allowed to localize the spin density within a macrobicyclic framework. CV of the cobalt(II) complex in the cathodic range contains one reversible wave assigned to the Co2+/+ redox couple with the reduced anionic cobalt(I)-containing species stabilized by the electronic effect of six strong electron-withdrawing chlorine substituents. The quasireversible character of the Fe2+/+ wave suggests that the anionic iron(I)-containing macrobicydic species undergo substantial structural changes and side chemical reactions after such metal-centered reduction.
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