Electrochemical, Spectroscopic, Structural, and Magnetic Characterization of the Reduced and Protonated α-Dawson Anions in [Fe(η5-C5Me5)2]5[HS2Mo18O62]·3HCONMe2·2Et2O and [NBu4]5[HS2Mo18O62]·2H2O1

Juraja, Suzy M.; Vu, Truc; Richardt, Peter J. S.; Bond, Alan M.; Cardwell, Terence J.; Cashion, J. D.; Fallon, Gary D.; Lazarev, G. G.; Moubaraki, Boujemaa; Murray, Keith S.; Wedd, Anthony G.

doi:10.1021/ic010780s

Cited by 21 publications

(7 citation statements)

References 29 publications

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“…The major challenge of this approach is the identification of reactive building blocks that can be obtained in solution at concentrations that allow the formation of more complex architectures without undergoing spontaneous rearrangement or isomerisation processes. [17][18][19][20][21][22] Recently, we have identified one facile route that allows the stabilisation of reactive building blocks in solution and indeed resulted in the isolation of novel cluster types in the solid state. Bulky organic cations were used to kinetically stabilise and encapsulate metastable intermediates and prevent further rearrangement into thermodynamically favoured, well-known structures.…”

Section: Introductionmentioning

confidence: 99%

“…Bulky organic cations were used to kinetically stabilise and encapsulate metastable intermediates and prevent further rearrangement into thermodynamically favoured, well-known structures. [17][18][19][20] By using this approach, a highly charged low-symmetry {Mo 16 10À , was previously isolated. [21] The {Mo 16 } cluster is stable in the solid state and it was shown that the highly negative anion is virtually completely wrapped by the organic counterions.…”

Section: Introductionmentioning

confidence: 99%

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Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Streb

McGlone

Brücher

et al. 2008

Chemistry A European J

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A set of four hybrid host-guest complexes based on the inorganic crown ether analogue [H12W36O120]12- ({W36}) have been isolated and characterised. The cluster anion features a central rigid binding site made up of six terminal oxygen ligands and this motif allows the selective binding of a range of alkali and alkali-earth-metal cations. Here, the binding site was utilised to functionalise the metal oxide-based cavity by complexing a range of protonated primary amines within the recognition site. As a result, a set of four hybrid organic-inorganic host-guest complexes were obtained whereby the interactions are highly directed specifically within this cavity. The guest cations in these molecular assemblies range from the aromatic 2-phenethylamine (1) and 4-phenylbutylamine (2) to the bifunctional aromatic p-xylylene diamine (3) and the aliphatic, bifunctional 1,6-diaminohexane (4). Compounds 1-4 were structurally characterised by single-crystal X-ray diffraction, elemental analysis, flame atomic absorption spectroscopy, FTIR and bond valence sum calculations. This comparative study focuses on the supramolecular effects of the amine guest cations and investigates their structure-directing effects on the framework arrangement arising by locking the protonated amines within the cavity of the {W36} cluster. It was shown that parts of the organic guest cation protrude from the central binding cavity and the nature of this protruding organic "tail" directs the solid-state arrangement of compounds 1-4. Guest cations with a hydrophobic phenyl tail result in an antiparallel assembly of {W36} complexes arranged in a series of pillared layers. As a consequence, no direct supramolecular interactions between {W36} clusters are observed. In contrast, bifunctional guest cations with a secondary amino binding site act as molecular connectors and directly link two cluster units thus locking the supramolecular assembly in a tilted arrangement. This direct linking of {W36} anions results in the formation of an infinite supramolecular scaffold.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Streb

McGlone

Brücher

et al. 2008

Chemistry A European J

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“…However, the band at lower energy (ca. 640 nm) is exclusive for 1 and may be ascribed to an intermolecular charge-transfer transition between ferrocenyl donors and POM acceptors [19,21] since none of its constituents exhibit any absorption in this range.…”

Section: Resultsmentioning

confidence: 99%

“…The structural analysis of such compounds has been revealed as a key factor for the identification of potential interesting properties and therefore, an extensive work has been dedicated to the single-crystal structure resolution of compounds combining Fc + or Fc* + units with POM clusters of very different nature. These include fully-oxidized or partially reduced [H x XM 12 O 40 ] n− Keggin-type plenary polyoxomolybdates (X = Si, Ge, P, As; H = 0–1) [14,15,16,17] or –tungstates (X = Si, Fe III ; H = 0–1) [17], first-row transition metal mono-substituted [HPCu(H 2 O)W 11 O 39 ] 4− Keggin or [Cr(OH) 6 Mo 6 O 18 ] 3− Anderson–Evans paramagnetic anions [18] and redox-active [HS 2 Mo 18 O 62 ] 5− Wells–Dawson-type species [19]. Some authors have opted for the organic derivatization of ferrocene units with positively-charged functional groups to lead to ammonium [20] or phosphonium [21] cations that can act as acceptors in the formation of CT salts with Keggin [22] or [M 6 O 19 ] 2− Lindqvist–type POMs (M = Mo, W) [23].…”

Section: Introductionmentioning

confidence: 99%

A Charge-Transfer Salt Based on Ferrocene/Ferrocenium Pairs and Keggin-Type Polyoxometalates

et al. 2018

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A new hybrid inorganic-organometallic salt has been obtained from the reaction of the Keggin-type silicotungstate anion with ferrocene in a water/methanol mixture as a result of the partial oxidation of ferrocene molecules to ferrocenium cations. Single-crystal X-ray diffraction analysis reveals the presence of four ferrocenium (FeIII) cations and one ferrocene (FeII) molecule per plenary Keggin anion in the crystal structure of [FeIII (Cp)2]4[SiW12O40]·[FeII(Cp)2]·2CH3OH (1). Compound 1 thus constitutes the first example in the literature in which ferrocenium and ferrocene species coexist in the structure of a polyoxometalate-based salt. The two crystallographically independent ferrocenium species in the asymmetric unit of 1 exhibit different configurations: One displays an eclipsed conformation with ideal D5h symmetry, whereas the conformation in the other one is staggered D5d. The crystal packing of 1 can be best described as an organometallic sub-lattice of ferrocenium and ferrocene species linked by a network of π-π interactions that generates rectangular cavities of about 14 × 10 Å in which strings of Keggin anions and methanol molecules are hosted, further connected to each other via weak OPOM···CMeOH-OMeOH···OPOM type hydrogen bonds. The charge-transfer nature of the salt has been studied by solid-state diffuse reflectance UV-Vis spectroscopy and the presence of magnetically isolated FeIII/FeII centres has been confirmed by Mössbauer spectroscopy. A topological study carried out on all of the pristine ferrocenyl species deposited in the Cambridge Structural Database (CSD) has allowed two main conclusions to be drawn: (1) these species tend to adopt extreme conformations (either eclipsed or staggered) with less than a 15% of examples showing intermediate states and (2) the oxidation state of the iron centres can be unequivocally assigned on the basis of a close inspection of the Fe···Cp distances, which allows ferrocene neutral molecules and ferrocenium cations to be easily distinguished.

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“…S5), † and then the plot displayed a deviation from linear Curie-Weiss (c ¼ C/(T À q)) behaviour, which was attributed to the temperature independent paramagnetism (TIP) resulting from the polyoxometalate cluster. [23][24][25][26] Interestingly, these two Mo(V) heteropoly blues of two-electron reduction were not magnetic silence at room temperature, but their antiferromagnetic interactions strongly increased with decreasing temperature to full spin antiparallel coupling at 2 K.…”

mentioning

confidence: 99%

Multidimensional frameworks constructed from Keggin-type heteropoly blue of molybdenum–tungsten cluster

Wang

Jiang

et al. 2011

CrystEngComm

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Electrochemical, Spectroscopic, Structural, and Magnetic Characterization of the Reduced and Protonated α-Dawson Anions in [Fe(η⁵-C₅Me₅)₂]₅[HS₂Mo₁₈O₆₂]·3HCONMe₂·2Et₂O and [NBu₄]₅[HS₂Mo₁₈O₆₂]·2H₂O¹

Cited by 21 publications

References 29 publications

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

Hybrid Host–Guest Complexes: Directing the Supramolecular Structure through Secondary Host–Guest Interactions

A Charge-Transfer Salt Based on Ferrocene/Ferrocenium Pairs and Keggin-Type Polyoxometalates

Multidimensional frameworks constructed from Keggin-type heteropoly blue of molybdenum–tungsten cluster

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