Mixed-valence phosphato–hydrogenphosphato–iron network compounds1∞{[C4N2H11.6]1.5[FeIIFeIII(PO4)(H0.8PO4)2]·H2O} and3∞[FeII5FeIII2(PO4)2(H0.5PO4)4]: structure elucidation with the help of Mössbauer spectroscopy and a caveat on X-ray diffraction

Abu‐Shandi, Khalid; Winkler, H.; Gerdan, Michael; Emmerling, Franziska; Wu, Biao; Janiak, Christoph

doi:10.1039/b301610b

Cited by 13 publications

(14 citation statements)

References 71 publications

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“…[62d-g] Apart from the simple one-dimensional structures, there are other one-dimensional structures possessing small metal-oxygen cluster units are also known. [63] In [C 4 Compared to the one-dimensional structures, there appears to be considerable variety and diversity in the twodimensional structures. [65][66][67][68][69][70][71][72] The use of fluoride ions in the synthesis has given rise to many interesting layered structures, especially those containing scandium, [65] iron, [69] zirconium, [71] and niobium.…”

Section: Phosphatesmentioning

confidence: 99%

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Open‐Framework Structures of Transition‐Metal Compounds

2008

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Inorganic framework solids are no longer limited to just the silicates and phosphates. Recent research has revealed that carboxylates, arsenates, sulfates, selenates, selenites, germanates, phosphites can also form such structures. One of the emerging areas combines the rich coordination chemistry of the central metal ions of many of these structures with the flexibility and functionality of the organic linkers to give rise to organic-inorganic hybrid compounds. The compounds of the transition-metals appear to provide many variations arising from their coordination preferences, ligand geometry, and the valence state. In addition, the combination of the magnetic nature of the transition metal center with the channel structure of open frameworks suggests interesting potential applications. In this Review the synthesis, structures and properties of the various transition-metal open-framework compounds are discussed.

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Section: Phosphatesmentioning

confidence: 99%

“…[62d-g] Apart from the simple one-dimensional structures, there are other one-dimensional structures possessing small metal-oxygen cluster units are also known [63]. Many compounds of transition-metal elements form this type of structure, especially titanium,[62a] vanadium,[62b,c] and iron.…”

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confidence: 99%

Open‐Framework Structures of Transition‐Metal Compounds

2008

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“…The finding of a Fe II and Fe III site for both Fe1 and Fe2 leads to the interpretation of 2 as a trapped mixed-valence system on the time scale of a Mössbauer experiment of 10 Ϫ7 s [13]. We see no intervalence transition between Fe II and Fe III , that is, no detrapping of the localized valence states [11,14]. The ratio of the relative areas A Fe(III) /A Fe(II) is about 2.8:1 which is higher than the ratio of 2:1 for the different iron sites seen in the crystal structure (see below).…”

Section: Resultsmentioning

confidence: 54%

“…The proton in the hydrogen-bisphosphonate (H-1) 2Ϫ oxidizes part of the Fe II to Fe III to give the ligand as 1 3Ϫ . Since the occupation factors of any protic hydrogen atoms and the Fe oxidation states are closely related [11], the single-crystal X-ray structure refinement alone usually cannot lead to an unambiguous formula assignment but needs the support by a 57 Fe Mössbauer study. The Mössbauer spectrum of 2 at room-temperature and 77 K ( Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1a and b) can be fitted by four doublets, two narrow ones which can be assigned to high-spin Fe III (S ϭ 5/2) and two wide ones assigned to high-spin Fe II (S ϭ 2) for both of which the observed isomer shifts and quadrupole splittings ( Table 1) are typical. Subspectra with isomer shifts δ α-Fe below 0.7 mm s Ϫ1 are assigned to Fe III , those above 1 mm s Ϫ1 to Fe II [4,11,12]. The decrease in the isomer shifts from 77 K to RT follows from the second-order Doppler shift (SOD).…”

Section: Resultsmentioning

confidence: 99%

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Structure and Mössbauer Study of the First Mixed‐Valence Iron Diphosphonate: $^{2}_{\infty}[\rm \{Fe^{II/III}(H_{2}O)_{2}\}\{Fe^{III/II}Cl\}_{2}(\mu_{4}-O_{3}P-C(OH)\{(CH_{2})_{4}NH_{3}\}-PO_{3})_{2}]\cdot4H_{2}O$

Abu‐Shandi

Winkler

Janiak

2006

Zeitschrift anorg allge chemie

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The title compound bis(µ 4 -5-ammonio-1-hydroxypentylidene-1,1-bisphosphonato-κ 7 O, OЈ,OЉ,Oٞ,OЈ v aquairon)-di(chloroiron)(II/III)-tetrahydrate was prepared by hydrothermal synthesis and consists of nets of corner sharing {FeO 6 } or {FeClO 5 } octahedra linked by {CPO 3 } tetrahedra. Neighboring layers interdigitate with their ammoniopentylidene tails and connect to a three-dimensional network by N-H···O and O(hydrate)-H···O hydrogen bonds. The ligand [PO 3 -C(OH){(CH 2 ) 4ϩ NH 3 }-PO 3 ] 3Ϫ is a zwitter-ion of overall charge Ϫ3. Different from other 629 known iron diphosphonates, which contain only either Fe II or Fe III , the iron bisphosphonate here is found from Mössbauer-Spectroscopy to be a trapped mixed-valence system with Fe II and Fe III disordered over both crystallographic sites Fe1 and Fe2 in what could be described as a coherent superposition of different states. At 4.2 K the Fe III is completely magnetically ordered.

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Offene Gerüststrukturen von Übergangsmetallen

Natarajan

Mandal

2008

Angewandte Chemie

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In den letzten Jahren hat sich gezeigt, dass neben anorganischen Silicaten und Phosphaten auch Carboxylate, Arsenate, Sulfate, Selenate, Selenite, Germanate und Phosphite offene Gerüststrukturen bilden können. Von besonderem Interesse sind die organisch‐anorganischen Hybridverbindungen, die sich aus der Kombination der reichen Koordinationschemie der zentralen Metall‐Ionen vieler dieser Strukturtypen mit der Flexibilität und der Funktionalität organischer Verbindungsglieder (“Linker”) ergeben. Vor allem die Übergangsmetalle scheinen besonders viele Varianten zu liefern, was in den bevorzugten Koordinationsweisen, Ligandengeometrien und Valenzzuständen begründet ist. Außerdem lässt die Kombination der magnetischen Eigenschaften von Übergangsmetallen mit den Kanalstrukturen offener Gerüste interessante Anwendungen erwarten. In diesem Aufsatz werden die Synthesen, Strukturen und Eigenschaften einer Reihe von Übergangsmetallverbindungen mit offenem Gerüst vorgestellt.

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Mixed-valence phosphato–hydrogenphosphato–iron network compounds¹_∞{[C₄N₂H_11.6]_1.5[Fe^IIFe^III(PO₄)(H_0.8PO₄)₂]·H₂O} and³_∞[Fe^II₅Fe^III₂(PO₄)₂(H_0.5PO₄)₄]: structure elucidation with the help of Mössbauer spectroscopy and a caveat on X-ray diffraction

Cited by 13 publications

References 71 publications

Open‐Framework Structures of Transition‐Metal Compounds

Open‐Framework Structures of Transition‐Metal Compounds

Structure and Mössbauer Study of the First Mixed‐Valence Iron Diphosphonate: $^{2}_{\infty}[\rm \{Fe^{II/III}(H_{2}O)_{2}\}\{Fe^{III/II}Cl\}_{2}(\mu_{4}-O_{3}P-C(OH)\{(CH_{2})_{4}NH_{3}\}-PO_{3})_{2}]\cdot4H_{2}O$

Offene Gerüststrukturen von Übergangsmetallen

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