The ferro/ferricyanide couple in an aluminum chloride-1-methyl-3-ethylimidazolium chloride ambient-temperature molten salt

Das, Basudev K.; Carlin, Richard T.; Osteryoung, R. A.

doi:10.1021/ic00302a011

Cited by 16 publications

(14 citation statements)

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“…Overall, we observed the same trend where reduction of [Fe III (CN) 6 ] 3− to [Fe II (CN) 6 ] 4− resulted in lowering the νCN frequency by 80 cm −1 in acetonitrile and 77 cm −1 in water. We attribute the offset in νCN frequencies of the acetonitrile and water dataset of approximately 13 cm −1 to solvent and counter cation effects 14 . Additionally, there is a minor shoulder feature at 2042 cm −1 which was attributed to adsorption of [Fe II (CN) 6 ] 4− to electrode surface in a previous SEC study 15 .…”

Section: Resultsmentioning

confidence: 99%

Electrochemical oxidation of ferricyanide

Cheah

Chernev

2021

Sci Rep

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We report the electrochemical oxidation of ferricyanide, [FeIII(CN)6]3− and characterised the oxidation product by in-situ FTIR and XAS spectroelectrochemistry methods. Oxidation of [FeIII(CN)6]3− is proposed to proceed via a tentative Fe(IV) intermediate that undergoes reduction elimination to give cis-[FeIII(CN)4(CH3CN)2]1− as stable product in acetonitrile. Speciation of the oxidation product by DFT calculations is underpinned by good agreement to experimental data.

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Section: Resultsmentioning

confidence: 99%

Electrochemical oxidation of ferricyanide

Cheah

Chernev

2021

Sci Rep

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“…Technical grade solvents were distilled prior to use. Tetrabutylammonium hexacyanoferrate(III) was prepared as described in literature . The ligands 3-methyl-9-oxo-2,4-di-(2-pyridyl)-7-(2-pyridylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester L 1 and 3-methyl-9-oxo-7-(2-pyridylmethyl)-2,4-di-(2-quinolyl)-3,7-diazabicyclo[3.3.1]-nonane-1,5-dicarboxylic acid dimethyl ester L 2 were obtained as described. − Caution!…”

Section: Methodsmentioning

confidence: 99%

Trinuclear {M¹}CN{M²}₂Complexes (M¹= Cr^III, Fe^III, Co^III; M²= Cu^II, Ni^II, Mn^II). Are Single Molecule Magnets Predictable?

et al. 2008

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The reaction of the hexacyanometalates K3[M(1)(CN)6] (M(1) = Cr(III), Fe(III), Co(III)) with the bispidine complexes [M(2)(L(1))(X)](n+) and [M(2)(L(2))(X)](n+) (M(2) = Mn(II), Ni(II), Cu(II); L(1) = 3-methyl-9-oxo-2,4-di-(2-pyridyl)-7-(2-pyridylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; L(2) = 3-methyl-9-oxo-7-(2-pyridylmethyl)-2,4-di-(2-quinolyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; X = anion or solvent) in water-methanol mixtures affords trinuclear complexes with cis- or trans-arrangement of the bispidine-capped divalent metal centers around the hexacyanometalate. X-ray structural analyses of five members of this family of complexes (cis-Fe[CuL(2)]2, trans-Fe[CuL(1)]2, cis-Co[CuL(2)]2, trans-Cr[MnL(1)]2, trans-Fe[MnL(1)]2) and the magnetic data of the entire series are reported. The magnetic data of the cyanide bridged, ferromagnetically coupled cis- and trans-Fe[ML]2 compounds (M = Ni(II), Cu(II)) with S = 3/2 (Cu(II)) and S = 5/2 (Ni(II)) ground states are analyzed with an extended Heisenberg Hamiltonian which accounts for anisotropy and zero-field splitting, and the data of the Cu(II) systems, for which structures are available, are thoroughly analyzed in terms of an orbital-dependent Heisenberg Hamiltonian, in which both spin-orbit coupling and low-symmetry ligand fields are taken into account. It is shown that the absence of single-molecule magnetic behavior in all spin clusters reported here is due to a large angular distortion of the [Fe(CN)6](3-) center and the concomitant quenching of orbital angular momentum of the Fe(III) ((2)T2g) ground state.

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“…The CN stretching frequency of a free CN À ion is 2080 cm À1 , whereas upon coordination to a metal ion, it shifts to higher frequencies, such as observed for (N(C 4 H 9 ) 4 ) 3 [M 0 (CN) 6 ]. 39,40 The IR spectra of 1a-6a show two characteristic absorption bands in the CN stretching region (Table 2): the high frequency bands can be attributed to the stretching of the CN ligand bridged between M 2+ and M 03+ in the M 2+ -CN-M 03+ mode and the low frequency bands can be assigned to the presence of the linkage isomer with the M 2+ -NC-M 03+ coordination mode, as it was reported for the bulk cyano-bridged coordination polymers. [41][42][43][44] It should be also noted that the IR spectra of the nanocomposites present the characteristic bands of the chitosan matrix.…”

Section: Synthesis Structural and Textural Characterizationsmentioning

confidence: 99%

Synthesis and studies of water-soluble Prussian Blue-type nanoparticles into chitosan beads

Folch

Larionova

Guari

et al. 2010

Phys. Chem. Chem. Phys.

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A new approach to the synthesis of highly stable aqueous colloids of coordination polymer nanoparticles was developed by using water-soluble chitosan beads as template and as stabilizing agent. The method consists in the synthesis of nanocomposite beads containing cyano-bridged coordination polymer nanoparticles via step-by-step coordination of the metal ions and the hexacyanometallate precursors into the chitosan pores and then water solubilization of these as-obtained nanocomposite beads. We obtain a large range of M(2+)/[M'(CN)(6)](3-)/chitosan (where M(2+) = Ni(2+), Cu(2+), Fe(2+), Co(2+), Mn(2+) and M' = Fe(3+) and Cr(3+)) nanocomposite beads and their respective aqueous colloids containing coordination polymer core/chitosan shell nanoparticles. The nanocomposite beads and the corresponding aqueous colloids were studied by Infrared (IR) and UV-Vis spectroscopy, nitrogen sorption (BET), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and magnetic analyses, which reveal the presence of homogeneously dispersed uniformly-sized cyano-bridged coordination polymer nanoparticles. The detailed studies of the static and dynamic magnetic properties of these nanoparticles show the occurrence of a spin-glass like behavior presumably produced by intra-particle spin disorder due to the low spin exchange energy characterizing these materials.

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The ferro/ferricyanide couple in an aluminum chloride-1-methyl-3-ethylimidazolium chloride ambient-temperature molten salt

Cited by 16 publications

References 2 publications

Electrochemical oxidation of ferricyanide

Electrochemical oxidation of ferricyanide

Trinuclear {M¹}CN{M²}₂Complexes (M¹= Cr^III, Fe^III, Co^III; M²= Cu^II, Ni^II, Mn^II). Are Single Molecule Magnets Predictable?

Synthesis and studies of water-soluble Prussian Blue-type nanoparticles into chitosan beads

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The ferro/ferricyanide couple in an aluminum chloride-1-methyl-3-ethylimidazolium chloride ambient-temperature molten salt

Cited by 16 publications

References 2 publications

Electrochemical oxidation of ferricyanide

Electrochemical oxidation of ferricyanide

Trinuclear {M1}CN{M2}2Complexes (M1= CrIII, FeIII, CoIII; M2= CuII, NiII, MnII). Are Single Molecule Magnets Predictable?

Synthesis and studies of water-soluble Prussian Blue-type nanoparticles into chitosan beads

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Trinuclear {M¹}CN{M²}₂Complexes (M¹= Cr^III, Fe^III, Co^III; M²= Cu^II, Ni^II, Mn^II). Are Single Molecule Magnets Predictable?