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Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

ABSTRACT: The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy.

SUBMITTER: Yambulatov DS

PROVIDER: S-EPMC8158106 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

Yambulatov Dmitriy S DS Nikolaevskii Stanislav A SA Kiskin Mikhail A MA Kholin Kirill V KV Khrizanforov Mikhail N MN Budnikova Yulia G YG Babeshkin Konstantin A KA Efimov Nikolay N NN Goloveshkin Alexander S AS Imshennik Vladimir K VK Maksimov Yurii V YV Kadilenko Evgeny M EM Gritsan Nina P NP Eremenko Igor L IL

Molecules (Basel, Switzerland) 20210518 10

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magne ...[more]

PMID: 34070061

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Project description:Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [H3tpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [FeIIItpfc(py)]2COT and 6-coordinate [FeIIItpfc(py)2]2COT, with one and two axial pyridine ligands per metal, respectively. X-Ray crystallography reveals a dome-shaped structure for [FeIIItpfc(py)]2COT and a perfectly planar geometry which (surprisingly at first) is also characterized by shorter Fe-N (corrole) and Fe-N (pyridine) distances. Computational investigations clarify that the structural phenomena are due to a change in the iron(III) spin state from intermediate (S = 3/2) to low (S = 1/2), and that both the 5- and 6-coordinated complexes are enthalpically favored. Yet, in contrast to iron(III) porphyrins, the formation enthalpy for the coordination of the first pyridine to Fe(III) corrole is more negative than that of the second pyridine coordination. Possible interactions between the two corrole subunits and the chelated iron ions were examined by UV-Vis spectroscopy, electrochemical techniques, and density functional theory (DFT). The large differences in the electronic spectra of the dimer relative to the monomer are concluded to be due to a reduced electronic gap, owing to the extensive electron delocalization through the fusing bridge. A cathodic sweep for the dimer discloses two redox processes, separated by 230 mV. The DFT self-consistent charge density for the neutral and cationic states (1- and 2-electron oxidized) reveals that the holes are localized on the macrocycle. A different picture emerges from the reduction process, where both the electrochemistry and the calculated charge density point toward two consecutive electron transfers with similar energetics, indicative of very weak electron communication between the two redox active iron(III) sites. The binuclear complex was determined to be a much better catalyst for the electrochemical hydrogen evolution reaction (HER) than the analogous mononuclear corrole.

Dataset Information

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

Publications

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

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