Crystal structure of hexacyano cobaltate(III) of caesium and tetramethylammonium: Cs[(Me)4N]2Co(CN)6

Morales, Angel Dago; Romero, René Guardiola; Rodríguez, Julio Duque; Hernández, R. Pomés; Bertrán, José Fernández

doi:10.1007/bf01023896

Cited by 9 publications

(7 citation statements)

References 8 publications

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“…Furthermore, from R1 to 4 , the IR bands broaden, probably due to an increase of the structural disorder induced by the simultaneous presence of cobalt atoms with different first neighbor bond-lengths in the structure. Indeed, for Co II (HS) L 6 (L = O/N), the Co-L mean distance is around 2.08 Å, , whereas it is 1.91 Å for Co III (BS) L 6 (L = O/N). ,, Besides, this band is not so broad in the spectrum of compound R2 , which mainly contains Fe II −CN−Co III pairs, that is to say a majority of Co−L short bonds.…”

Section: Resultsmentioning

confidence: 96%

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

et al. 2001

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We synthesized a series of CoFe Prussian blue analogues along which we tuned the amount of cesium cations inserted in the tetrahedral sites of the structure. Structure and electronic structure have been investigated, combining XANES, infrared spectroscopy, powder X-ray diffraction experiments, and magnetization measurements. The change of the magnetization induced by light along the series shows that the efficiency of the photoinduced magnetization, evidenced a few years ago in similar compounds by Hashimoto et al. (Sato, O.; Iyoda, T.; Fujishima, A.; Hashimoto, K. Science 1996, 272, 704-705; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Electrochem. Soc. 1997, 144, L11-L13; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Phys. Chem. B 1997, 101, 3903-3905; Einaga, Y.; Ohkoshi, S.-I.; Sato, O.; Fujishima, A.; Hashimoto, K. Chem. Lett. 1998, 585-586; and Sato, O.; Einaga, Y.; Fujishima, A.; Hashimoto, K. Inorg. Chem. 1999, 38, 4405-4412), depends on a compromise between the number of excitable diamagnetic pairs and the amount of [Fe(CN)6] vacancies giving the network flexibility. Besides the efficiency of the photoinduced process, the amount of [Fe(CN)6] vacancies also controls a thermally induced electron transfer.

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Section: Resultsmentioning

confidence: 96%

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

et al. 2001

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“…Nevertheless, quantitative information on the coordination sphere of the cobalt atom can be extracted from peak 1. To do that, we calculate the EXAFS signals for cobalt octahedral environments: 6 O/N neighbors at 2.08 Å, typical distance for HS Co II ions, and 6 O/N neighbors at 1.91 Å, typical distance for LS Co III ions. , These distances were also obtained by Hashimoto et al for analogues compounds . EXAFS signals have been calculated in the single scattering approximation with amplitude and phase shift functions calculated by the FEFF7 code for an octahedral CoN 6 cluster (Co−N = 1.91 Å) .…”

Section: Cobalt K-edge: Results and Discussionmentioning

confidence: 99%

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 2. X-ray Absorption Spectroscopy of the Metastable State

et al. 2000

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A CoFe Prussian blue analogue Rb 1.8 Co 4 [Fe(CN) 6 ] 3.3 ‚13H 2 O was synthesized, which presents an important photomagnetic effect. The electronic structure and the local structure of the ground and of the excited states have been investigated. X-ray absorption spectroscopy measurements at the Co and Fe L 2,3 edges and cobalt K-edge (XANES and EXAFS) evidence the local electronic transfer and the spin change of the cobalt ions induced by irradiation. We observed a 0.19 Å increase of the Co-N bond length, associated with the transformation of Co III low spin to Co II high spin. The Co II /Co III ratio has been evaluated as a function of the irradiation time and revealed as an important parameter to understanding the bulk magnetic properties. The combined role of the diamagnetic Fe II -Co III pairs and hexacyanoferrate(III) vacancies is locally evidenced. This work is a new step in the understanding of the photoinduced electron transfer.

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“…; the structure for the latter was obtained in the solid state, 51 but the reference compound is a 1 M aqueous K 3 Co(CN) 6 solution. Taura has reported that the 59 Co chemical shift of aqueous K 3 Co(CN) 6 varies by more than 300 ppm, depending on solvent.…”

Section: àmentioning

confidence: 99%

Solid-state 13C and 59Co NMR spectroscopy of 13C-methylcobalt(iii) complexes with amine ligands

Ooms

Bernard

Kadziola

et al. 2009

Phys. Chem. Chem. Phys.

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Five octahedral Co(iii) cations, [trans-Co(en)(2)(X)((13)CH(3))](n+) where en = ethylenediamine, X = CN(-), N(3)(-), NH(3), NO(2)(-) or H(2)O and n = 1 or 2, as well as [Co(NH(3))(5)(13)CH(3)](2+), have been investigated by solid-state (13)C and (59)Co NMR spectroscopy. We show that the determination of the (59)Co nuclear quadrupolar parameters both directly via(59)Co NMR and indirectly via(13)C NMR provide complementary information that is unavailable if one investigates only one nucleus. Specifically, (1)J((59)Co,(13)C) and the orientation of the largest component of the EFG were determined via(13)C NMR spectroscopy, which also established the negative sign of C(Q)((59)Co). Cobalt-59 NMR spectroscopy was used to characterize the cobalt magnetic shielding tensor, to verify the magnitudes of C(Q)((59)Co) and to establish the value of eta(Q), which is difficult to determine indirectly. The measurements show that the EFG tensors are either axially symmetric or close to being so, but there is a wide range of C(Q) values, from -40 MHz for the complex with X = H(2)O to -105 MHz with X = CN(-). The Co chemical shift tensors are approximately axially symmetric with the spans, delta(11)-delta(33), ranging from 3700 to 5600 ppm for X = H(2)O and CN(-), respectively. The latter measurements also established the relative orientations of the Co EFG and chemical shift tensors. Density functional theory calculations of the (59)Co EFG and magnetic shielding tensors as well as of (1)J((59)Co,(13)C) for the NO(2)(-) and N(3)(-) complexes were undertaken. These calculations confirm the experimental observation that the sign of C(Q) is negative and that the largest component of the EFG is along the Co-methyl-carbon bond.

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Crystal structure of hexacyano cobaltate(III) of caesium and tetramethylammonium: Cs[(Me)4N]2Co(CN)6

Cited by 9 publications

References 8 publications

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 2. X-ray Absorption Spectroscopy of the Metastable State

Solid-state 13C and 59Co NMR spectroscopy of 13C-methylcobalt(iii) complexes with amine ligands

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Crystal structure of hexacyano cobaltate(III) of caesium and tetramethylammonium: Cs[(Me)4N]2Co(CN)6

Cited by 9 publications

References 8 publications

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues CIxCo4[Fe(CN)6]y (CI = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)6] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues CIxCo4[Fe(CN)6]y (CI = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)6] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues CIxCo4[Fe(CN)6]y (CI = Alkali Cation). 2. X-ray Absorption Spectroscopy of the Metastable State

Solid-state 13C and 59Co NMR spectroscopy of 13C-methylcobalt(iii) complexes with amine ligands

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Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)₆] Vacancies in Cesium Derivatives

Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C^I_xCo₄[Fe(CN)₆]_y (C^I = Alkali Cation). 2. X-ray Absorption Spectroscopy of the Metastable State