Contribution to the coordination chemistry of transition metal nitroprussides: a cryo-XPS study

Cano, A.; Lartundo-Rojas, L.; Shchukarev, Andrey; Reguera, E.

doi:10.1039/c9nj00141g

Cited by 65 publications

(61 citation statements)

References 49 publications

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“…Based on these facts, the effective valence for the iron atom in the nitroprusside complex ion does not correspond to a divalent species. According to the XPS Fe 2p 3/2 binding energy, its effective valence is similar to the one expected for an Fe IV species …”

Section: Resultssupporting

confidence: 60%

“…No appreciable variation was observed for the Fe–N CN distance. Relative to other transition metal cyanides, the electron density on the N ends of nitroprussides is significantly lower due to the strong π‐back donation for the nitrosyl group (NO) . This results in a weak Fe–N CN bonding interaction, which probably explains the low sensibility of that bond to the spin transition.…”

Section: Resultsmentioning

confidence: 99%

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Thermally Induced Spin Transition in a 2D Ferrous Nitroprusside

et al. 2019

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This study reports the intercalation of pyridine molecules between neighboring layers of two-dimensional (2D) ferrous nitroprusside. In the material under study, the stacking of neighboring layers results in the formation of a long range ordered solid, where the 3D structure is supported by dipoledipole attractive interactions between neighboring pyridine molecules in the interlayer region. No chemical interactions were observed between layers, which preserve their identity as a 2D material. In this hybrid inorganic-organic solid, a thermal induced spin transitions from high to low spin on cooling and [a] 4967 [a] The values of δ are reported relative to sodium nitroprusside at 300 K; The fitting error for δ and Δ is no higher than 0.001 mm/s, and it remains below 0.01 mm/s for the value of Γ; Py =pyridine; LS = low spin; HS = high spin.

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Section: Resultssupporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Thermally Induced Spin Transition in a 2D Ferrous Nitroprusside

et al. 2019

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“…The crystal structures, and spectroscopic and thermal properties of these 3D materials are documented. [16,21] To favor the selective rupture of the axial CNÀTb ond, samples of 3D transition metal nitroprussides were suspended in 1m2p at a concentration of 0.01 mg mL À1 in methanol solution and then sonicated for 1h.T he obtained suspension precipitates on aging as a fine powder,w hich was separated by centrifugation and washed several times with fresh 1m2p. The formed solid was characterized from IR, Raman, UV/Vis and Mçssbauer data, TG curves and magnetic measurements, and its crystal structure solved and refined from powder XRD patterns.…”

Section: Methodsmentioning

confidence: 99%

“…Compared with the equatorial CN ligands, the axial CN one of the nitroprusside buildingb lock, the [Fe(CN) 5 NO] 2À anion, has al ower electron density on the N end, and from this, the formation of aw eaker coordination bond with transition metals results. [16] 1m2p is an aprotic dipolars olventw ith an extremely large surface tension, above4 0mJm À2 ,a nd this explains its application in exfoliating process of 2D materials, among them, graphenea nd its derivatives, transition metal chalcogenides,a nd transition metal oxides. [17] 1m2p has the ability to minimize the energyr equiredt oe xfoliate these materials.…”

Section: Introductionmentioning

confidence: 99%

From 3D to 2D Transition Metal Nitroprussides by Selective Rupture of Axial Bonds

Ávila

Osiry

Plasencia

et al. 2019

Chemistry A European J

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1-methyl-2-pyrrolidone( 1m2p)i sasolvent with proven abilitiesf or 2D-solid exfoliation due to its extremely high surface tension. In principle, such af eature could be used also to induce the selectiveb reaking of certain bonds in solids to obtain new materials. Such ah ypothesis is demonstrated in this study for transition metal nitroprussides, where 2D solids are obtained from 3D frameworks by selective rupture of axial bonds. This contribution discusses the mechanism involved in such molecular manufacture. The crystal structuref or the formed 2D solids was solved and refined from XRD powder patterns recordedu sing synchrotron radiation.M çssbauer,I Ra nd Ramans pectrap rovided fine details on the electronic structure of the resulting new series of layered materials. The experimental information was complemented with calculations for the molecule configuration in its non-activated and activated forms. In the obtained 2D solids,n eighboring layers of about 1nmo ft hickness remain separated by activated1 m2p molecules. The interaction betweenn eighboring layers is of ap hysicaln ature, withoutt he presence of ac hemical bond between them,a sc orresponds to a2Dm aterial.For 1m2p: n(C =O) = 1688 cm À1 and n(NÀC CH3 ) = 1402 cm À1 ;[ a] Ta ken from Raman spectrum.

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“…XPS senses the binding energy for the core‐level electrons of a given atom. The binding energy for the atom inner electrons is slightly affected by the level of occupation of its outer orbitals, which, in turn, is determined by charge transfer processes, polarization of the electron clouds, coordination number, and bonding interactions with neighboring atoms . This suggests that XPS is not merely a complement for the IR data, it provides additional information, including being a direct sensor for the charge density located on a given atom, through the corresponding value for the binding energy (BE), under the hypothesis that it is determined by the initial effects during the photoelectron emission.…”

Section: Introductionmentioning

confidence: 98%

Charge Redistribution Effects in Hexacyanometallates Evaluated from XPS Data

et al. 2019

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The charge redistribution effects determine the physical and functional properties of transition metal hexacyanometallates. The π-back bonding interaction between the CN ligand and the metal (M) linked at its C end and the σ donation from the N end to a second transition metal (T), when a coordination polymer is formed, are relevant features of such effects. The π-back donation interaction contributes to the overlapping of the electron clouds of M and T metals in the ···-T-N≡C-M-C≡N-T-··· chain. In this contribution, we demonstrate that XPS spectroscopy is a useful tool to sense the change in the electron density redistribution in hexacyanometallates related to these two mechanisms. The results herein discussed contribute to understand the physical and chemical properties of these materials. Initially, a series of potassium salts, K n [M 6-n (CN) 6 ] (M = Cr III , Fe II , Ru II , Os II , Co III , Rh III , Ir III , Pt IV ) is considered in order to evaluate the role of the π-back donation on the electron density found at the N atom, which determines [a]

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Contribution to the coordination chemistry of transition metal nitroprussides: a cryo-XPS study

Abstract: The XPS Fe 2p3/2 core-level spectra of sodium hexacyanoferrate(ii) and sodium nitroprusside.

Cited by 65 publications

References 49 publications

Thermally Induced Spin Transition in a 2D Ferrous Nitroprusside

Thermally Induced Spin Transition in a 2D Ferrous Nitroprusside

From 3D to 2D Transition Metal Nitroprussides by Selective Rupture of Axial Bonds

Charge Redistribution Effects in Hexacyanometallates Evaluated from XPS Data

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