From Mesomorphic Phosphine Oxide to Clustomesogens Containing Molybdenum and Tungsten Octahedral Cluster Cores

Cı̂rcu, Viorel; Molard, Yann; Amela-Cortés, Maria; Bentaleb, Ahmed; Barois, P.; Dorcet, Vincent; Cordier, Stéphane

doi:10.1002/anie.201503205

Cited by 17 publications

(10 citation statements)

References 64 publications

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“…In general, octahedral clusters represent an important class of compounds in the field of solid-state chemistry . Nevertheless, sophisticated solution chemistry, ranging from coordination chemistry to supramolecular materials, can be also developed from octahedral-type clusters, making it possible to investigate a large panel of applications in photocatalysis, soft materials, bioimaging, or phototherapy …”

Section: Introductionmentioning

confidence: 99%

Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials

et al. 2017

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International audienceHerein, we report on a three-component supra molecular hybrid system built from specific recognition processes involving a Dawson-type polyoxometalate (POM) ,P2W18O62](6-), a cationic electron-rich cluster [Ta6Br12(H2O)(6)](2+), and gamma-cyclodextrin (gamma-CD). Such materials have been investigated using a bottom-up approach by studying the specific interactions between gamma-CD and both types of inorganic units. Their ability to interact has been investigated in the solid state by single-crystal X-ray diffraction (XRD) and in solution using multinuclear NMR methods (including DOSY, EXSY, and COSY), electrospray ionization mass and UV-vis spectroscopies, electrochemistry, and isothermal titration calorimetry experiments. Single-crystal XRD analysis reveals that POM:gamma-CD constitutes a highly versatile system which gives aggregates with 1:1, 1:2, and 1:3 stoichiometry. Surprisingly, these arrangements exhibit a common feature wherein the gamma-CD moiety interacts with the Dawson-type POMs through its primary face. We present also the first structural model involving an octahedral-type metallic cluster with gamma-CD. XRD study reveals that the cationic [Ta6Br12(H2O)(6)](2+) ion is closely embedded within two gamma-CD units to give a supramolecular ditopic cation, suitable to be used as a linker within extended structure. Solution study demonstrates clearly that pre-associations exist in solution, for which binding constants and thermodynamic parameters have been determined, giving preliminary arguments about the chaotropic nature of the inorganic ions. Finally, both building blocks, i.e., the ditopic supramolecular cation {[Ta6Br12(H2O)(6)]@2CD}(2+) and the Dawson-type anion, react together to give a three-component, well-ordered hybrid material derived either as a supramolecular hydrogel or single crystals. The solid-state structure shows an unprecedented helicoidal tubular chain resulting from the periodic alternation of POM and supramolecular cation, featuring short hydrogen-bonding contacts between the electron-poor POM and electron-rich cluster. The 1D tubular ionic polymer observed in the single crystals should make it possible to understand the long-range ordering observed within the hydrogel hybrid material. The supramolecular chemical complementarities between the gamma-CD-based ditopic cation and POM open a wide scope for the design of hybrid materials that accumulate synergistic functionalities

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Section: Introductionmentioning

confidence: 99%

Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials

et al. 2017

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“…isoelectronic to {Re 6 Q 8 } 2+ species, are generally far less studied, despite the recent data that suggests these complexes can also be highly luminescent. [44][45][46][47] In this work we compare optical and XEOL properties of octahedral tungsten complexes: (…”

Section: Introductionmentioning

confidence: 99%

A comparative study of optical properties and X-ray induced luminescence of octahedral molybdenum and tungsten cluster complexes

et al. 2017

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Octahedral metal cluster complexes have high potential for biomedical applications. In order to evaluate the benefits of these moieties for combined CT/X-ray luminescence computed tomography, this paper compares photoluminescence, radiodensity and X-ray induced luminescence properties of eight related octahedral molybdenum and tungsten cluster complexes [{MI}L] (where M is Mo or W and L is I, NO, OTs or OH/HO). This article demonstrates that despite the fact that molybdenum cluster complexes are better photoluminescence emitters, tungsten cluster complexes, in particular (BuN)[{WI}I], demonstrate significantly higher X-ray induced luminescence due to a combination of relatively good photoluminescence properties and high X-ray attenuation. Additionally, photo-degradation of [{MI}(NO)] was evaluated.

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“…Mesogene, die als Hybride zwischen anorganischen Zentren und organischer Peripherie konzipiert sind, stellten Cordier und Mitarbeiter vor. 12) Sie organisierten Metallcluster M 6 Cl 6 4+ (CF 3 SO 3 -) 4 (M = Mo, W; X = Br, Cl) durch neue Phosphinoxidmesogene (11) in smektischen LC-Phasen. Die Cluster behielten ihre lichtemittierenden Eigenschaften in der Flüssigkristallphase.…”

Section: Siliciumrhodaminderivate Weisenunclassified

Organische Chemie

Itzen¹,

Schaschke²,

Beifuß³

et al. 2016

Nachr Chem

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From Mesomorphic Phosphine Oxide to Clustomesogens Containing Molybdenum and Tungsten Octahedral Cluster Cores

Cited by 17 publications

References 64 publications

Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials

Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials

A comparative study of optical properties and X-ray induced luminescence of octahedral molybdenum and tungsten cluster complexes

Organische Chemie

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