Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue:  Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies

Franz, Patrick; Ambrus, Christina; Hauser, Andreas; Chernyshov, Dmitry; Hostettler, Marc; Hauser, Jürg; Keller, L.; Krämer, Karl; Stœckli-Evans, Helen; Pattison, Philip; Bürgi, Hans‐Beat; Decurtins, Silvio

doi:10.1021/ja0465451

Cited by 57 publications

(39 citation statements)

References 37 publications

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“…Short-range correlations could be evidenced through diffuse scattering but good quality single-crystal diffraction data are necessary to analyze such effects ͑see Ref. 43 for instance͒.…”

Section: Discussionmentioning

confidence: 99%

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

et al. 2009

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Cobalt hexacyanoferrates, which exhibit thermally induced and photo-induced spin transitions, have been extensively studied as model materials for molecular-based photomagnetic solids. Synchrotron x-ray diffraction ͑XRD͒ experiments combined with magnetic measurements were used here to get some new insights in their diagram of phase transformation. For a Na 0.32 Co͓Fe͑CN͒ 6 ͔ 0.74 · 3.4H 2 O sample composition, the hightemperature ͑HT͒ phase could be efficiently trapped by rapid cooling, thus allowing a comparison with the photo-induced phase directly formed at low temperature by light irradiation. In terms of magnetic behavior, the two metastable phases strongly differ with lower critical temperature and magnetization values but higher decay temperature for the HT quenched phase. As only a slight change in the lattice constant with no symmetry breaking is reported from XRD, the differences between the two phases are discussed on the basis of local and disordered tilting of the ͓Fe͑CN͒ 6 ͔ polyhedral units.

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“…Short-range correlations could be evidenced through diffuse scattering but good quality single-crystal diffraction data are necessary to analyze such effects ͑see Ref. 43 for instance͒.…”

Section: Discussionmentioning

confidence: 99%

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

et al. 2009

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“…Articles within different fields of physics and chemistry demonstrate the broad and continued interest in exchange interactions in transition metal pairs. Published studies on Ni 2+ -Mn 2+ (Ferguson et al 1966a), Cu 2+ -Mn 2+ (Ferre and Regis 1978;Cador et al 2000), Mn 2+ -Mn 3+ (Franz et al 2004;Cox et al 2011;Xie et al 2012), Mn 3+ -Mn 3+ (Pelletier and Reber 1995), and Mn 3+ -Mn 4+ pairs (Birkelbach et al 1998) are some examples that reflect this interest.…”

Section: Optical Absorption Spectroscopymentioning

confidence: 98%

Color of Mn-bearing gahnite: A first example of electronic transitions in heterovalent exchange coupled IVMn2+-VIMn3+ pairs in minerals

Hålenius

Bosi

2014

American Mineralogist

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A natural yellow and transparent crystal of Mn-bearing, Mg-rich gahnite (ZnAl 2 O 4 ) from Nordmark (Sweden) was studied by electron microprobe, single-crystal X-ray diffraction and optical absorption spectroscopy. The empirical structural formula of the crystal, T (Zn 0.52 Mg 0.34 Mn 2+ 0.08 Al 0.06 ) S1.00 M (Al 1.88 Mn 3+ 0.06 Fe 3+ 0.01 Mg 0.04 Mn 2+ 0.01 ) S2.00 O 4 , shows that Mn 2+ and Mn 3+ are almost completely ordered at the T and M sites, respectively. The electronic absorption spectrum of the spinel shows, in addition to a strong UV-absorption edge (O 2--Mn 3+ and O 2--Fe 3+ ligand-metal charge transfers) and two broad VI Mn 3+ -bands, a set of relatively narrow absorption bands at energies comparable to those caused by spin-forbidden electron transitions in tetrahedrally coordinated Mn 2+ in oxide spinel. However, the set of bands in the present spectrum is shifted to lower energies and they are intensified by approximately an order of magnitude compared to those recorded for spin-forbidden IV Mn 2+ -bands in spinel. These characteristic differences in combination with the determined cation distribution in the present gahnite demonstrates that electronic transitions in exchange coupled IV Mn 2+ -VI Mn 3+ pairs cause its color.

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“…Although most structural studies have been carried out on powder samples, there are at least three PBAs of type 1 [21] and a dozen of type 2 [22] (including the diamagnetic Cd II 3 A C H T U N G T R E N N U N G [Co III (CN) 6 ] 2 ·H 2 O (1) [23] and the paramagnetic Cd II 3 -A C H T U N G T R E N N U N G [Fe III (CN) 6 ] 2 ·H 2 O (5) [24] compounds) that have been characterised by single-crystal X-ray experiments. For the PBAs of type 2, the long-range averaged order obtained through Xray diffraction leads to the high symmetry space group Fm3m.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

“…For the PBAs of type 2, the long-range averaged order obtained through Xray diffraction leads to the high symmetry space group Fm3m. [22] However, the microscopic description is unequivocal: 1) vacancies may be ordered in the solid in such a way that only divalent sites with neutral charge…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Probing Spin Density and Local Structure in the Prussian Blue Analogues CsCd[Fe/Co(CN)₆]⋅0.5 H₂O and Cd₃[Fe/Co(CN)₆]₂⋅15 H₂O with Solid‐State MAS NMR Spectroscopy

Flambard

Köhler

Lescouëzec

et al. 2011

Chemistry A European J

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Magic-angle spinning (MAS) NMR spectroscopy is used to study the local structure and spin delocalisation in Prussian blue analogues (PBAs). We selected two common archetypes of PBAs (A(I)M(II)[M(III)(CN)(6)]·xH(2)O and M(II)(3)[M(III)(CN)(6)](2)·xH(2)O, in which A(I) is an alkali ion, and M(II) and M(III) are transition-metal ions) that exhibit similar cubic frameworks but different microscopic structures. Whereas the first type of PBA contains interstitial alkali ions and does not exhibit any [M(III)(CN)(6)](3-) vacancies, the second type of PBA exhibits [M(III)(CN)(6)](3-) vacancies, but does not contain inserted alkali ions. In this study, we selected Cd(II) as a divalent metal in order to use the (113)Cd nuclei (I=1/2) as a probe of the local structure. Here, we present a complete MAS NMR study on two series of PBAs of the formulas Cd(II)(3)[Fe(III)(x)Co(III)(1-x)(CN)(6)](2)·15H(2)O with x=0 (1), 0.25 (2), 0.5 (3), 0.75 (4) and 1 (5), and CsCd(II)[Fe(III)(x)Co(III)(1-x)(CN)(6)]·0.5H(2)O with x=0 (6), 0.25 (7), 0.5 (8), 0.75 (9) and 1 (10). Interestingly, the presence of Fe(III) magnetic centres in the vicinity of the cadmium sites has a magnifying-glass effect on the NMR spectrum: it induces a striking signal spread such that the resolution is notably improved compared to that achieved for the diamagnetic PBAs. By doping the sample with varying amounts of diamagnetic Co(III) and comparing the NMR spectra of both types of PBAs, we have been able to give a view of the structure which is complementary to that usually obtained from X-ray diffraction studies. In particular, this study has shown that the vacancies are not randomly distributed in the mesoporous PBAs. Moreover the cadmium chemical shift, which is a measure of the hyperfine coupling, allows the estimation of the spin density on the cadmium nucleus, and consequently, the elucidation of the spin delocalisation mechanism in these compounds along with its dependency on structural parameters.

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Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies

Cited by 57 publications

References 37 publications

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

Color of Mn-bearing gahnite: A first example of electronic transitions in heterovalent exchange coupled IVMn2+-VIMn3+ pairs in minerals

Probing Spin Density and Local Structure in the Prussian Blue Analogues CsCd[Fe/Co(CN)₆]⋅0.5 H₂O and Cd₃[Fe/Co(CN)₆]₂⋅15 H₂O with Solid‐State MAS NMR Spectroscopy

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Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies

Cited by 57 publications

References 37 publications

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

Evidence for complex multistability in photomagnetic cobalt hexacyanoferrates from combined magnetic and synchrotron x-ray diffraction measurements

Color of Mn-bearing gahnite: A first example of electronic transitions in heterovalent exchange coupled IVMn2+-VIMn3+ pairs in minerals

Probing Spin Density and Local Structure in the Prussian Blue Analogues CsCd[Fe/Co(CN)6]⋅0.5 H2O and Cd3[Fe/Co(CN)6]2⋅15 H2O with Solid‐State MAS NMR Spectroscopy

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Probing Spin Density and Local Structure in the Prussian Blue Analogues CsCd[Fe/Co(CN)₆]⋅0.5 H₂O and Cd₃[Fe/Co(CN)₆]₂⋅15 H₂O with Solid‐State MAS NMR Spectroscopy