Synthesis, Structure, and Properties of New Hybrid Nanocomposites Containing the [Mo6( 3-Cl)8]4+Cluster

Golubeva, N. D.; Adamenko, O. A.; Boǐko, G. N.; Petrova, L. A.; Ol’khov, Yu. A.; Pomogailo, A. D.

doi:10.1023/b:inma.0000020534.96346.55

Cited by 14 publications

(4 citation statements)

References 11 publications

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“…On the subsequent workup of the ether mother liquor, the total yield of the product (a white crystalline solid) was 26.50 g (0.238 mol, 79.3%). 1 Bis(η η η η η 5 ethenylcyclopentadienyl)dichlorohafnium (5). A solu tion of cyclopentadienide 2 (4.45 g, 45.4 mmol) in 20 mL of THF was added at -20 °C under vigorous stirring to a solution of HfCl 4 (7.27 g, 22.7 mmol) in 30 mL of THF.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride

et al. 2005

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Novel vinyl and isopropenyl substituted cyclopentadienyl complexes of hafnium(IV), [C 5 H 4 (CR=CH 2 )] 2 HfCl 2 [R = H (5), CH 3 (6)], were prepared and characterized. The organo metallic monomers obtained were shown to undergo radical or anionic homopolymerization. Copolymerization of these metallocenes with styrene was performed. The potential applica tions of the metal polymers in question were considered.Organometallic polymers obtained by polymerization or copolymerization of appropriate monomers are of con siderable interest as immobilized catalysts for various re actions and as precursors for the preparation of nano composite materials, ceramics, and so on.However, the range of organometallic monomers in which the group capable of polymerization is directly bound to a transition metal atom through a metal-car bon bond is very limited, as these molecules are unstable. On the one hand, the average dissociation energy of a metal-carbon bond D(M-C) is comparable 2,3 with the average metal-halogen bond energy, D(M-Cl) or D(M-Br), even for the least stable alkyl derivatives of transition metals, but on the other hand, this bond is much more reactive than the M-O, M-N, M-Hal, etc. bonds. This is especially clear in the polymerization of such monomers because in the majority of cases, the syn thesis of metal containing polymers is accompanied by elimination of metal hydride: 4The undesirable β hydride transfer can be prevented by using organometallic compounds devoid of hydrogen at the β carbon atom. For this purpose, Me or another group is introduced instead of the H atom.Procedures for the synthesis of organometallic mono mers in which the Cp rings contain a vinyl or an iso propenyl group have been developed in sufficient detail for a number of metals. This is a rather well studied field of chemistry of polymers based on vinylferrocene, which is among the first monomers containing a chemically bound metal. The polymerization of metal monomers of this type can be initiated by any type of initiation (radical, cationic, anionic, Ziegler-Natta catalysts). Their sus ceptibility to a particular initiation type can be changed crucially by introducing appropriate substituents into the vinyl group. As an example, one can mention cyclo pentadienyl complexes containing the isopropenyl group instead of vinyl, which are potential monomers for cat ionic polymerization. 5 The purpose of this study is to prepare bis(vinyl cyclopentadienyl) and bis(isopropenylcyclopentadi enyl)dichlorohafnium as potential metal monomers and to attempt the synthesis of polymers and copolymers based on these monomers. Results and DiscussionSynthesis of Hf IV containing monomers. As the start ing monomers for the subsequent polymerization, we prepared two new hafnocene dichlorides, * For Part 58, see Ref. 1.

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Section: Methodsmentioning

confidence: 99%

Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride

et al. 2005

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“…The direct incorporation of inorganic species in the polymer has to be circumvented because strong interactions between the organic and inorganic entities constituting the hybrid materials are pre-requisite to obtain fully homogeneous and stable hybrid material [56,57]. The common methodology is based on the covalent grafting of up to six polymerizable units in apical positions of the inorganic cluster core [58][59][60][61][62][63][64].…”

Section: New Nanostructured Materials Based On Mo 6 Nanocluster For Optical Applicationsmentioning

confidence: 99%

Inorganic Molybdenum Octahedral Nanosized Cluster Units, Versatile Functional Building Block for Nanoarchitectonics

Cordier

Grasset

Molard

et al. 2014

J Inorg Organomet Polym

106

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International audienceRecently, Nanoarchitectonics has been introducedas a new concept that refers to a technology systemfor arranging nanoscale structural units in a requiredarchitecture. Multifunctional properties are achieved by acombination of several materials in a well-defined architecture.In the frame of this concept, composite nanoarchitecturesrepresent a new class of nanostructured entitiesthat integrate various dissimilar nanoscale building blocksincluding clusters, particles, wires and films. The heterogeneouscomposite nanostructured materials are composedby definition of multi-(nano)components, each tailored toaddress different requirements. As one of the nanocomponents,nanometer sized metal clusters (\2 nm), whichconsist of less than a few dozens of metal atoms, could bedefined as a link between atom and nanoparticle. In thispaper, we will focus on our results on new nano-compositesinvolving Mo6 atom nanosized cluster units for optical,nanobiotechnology, energy and environmental applications

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“…In that respect, polymethylmethacrylate (PMMA) emerged as one of the best polymeric dispersion matrices, owing to its good chemical and thermal stability, excellent biocompatibility and prominent transparency in the UV-NIR absorption range [38,39]. Luminescent Mo 6 @PMMA hybrid nanocomposites were prepared by in situ polymerization of vinyl acrylate containing metal cluster compounds [40–43] or by using supramolecular interactions between a ternary Cnormals2false[normalMo6I8i(OCOnormalC2normalF5)6afalse] (CMIF) clusters salt and PMMA partially functionalized by lateral poly(ethyleneoxide) chains [44]. Within such hybrid coating materials, the polymer matrix acted as a waveguide enabling both trapping the incident solar light and directing the light emitted by MC to its edges.…”

Section: Introductionmentioning

confidence: 99%

Transparent functional nanocomposite films based on octahedral metal clusters: synthesis by electrophoretic deposition process and characterization

et al. 2019

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Transparent optical thin films have recently attracted a growing interest for functional window applications. In this study, highly visible transparent nanocomposite films with ultraviolet (UV)-near-infrared (NIR)-blocking capabilities are reported. Such films, composed of Mo 6 and Nb 6 octahedral metal atom clusters (MC) and polymethylmethacrylate polymer (PMMA), were prepared by electrophoretic deposition on indium tin oxide-coated glass (ITO glass). PMMA was found to improve both the chemical and physical stability of Mo 6 and Nb 6 MCs, resulting in a relatively homogeneous distribution of the clusters within the PMMA matrix, as seen by microstructural observations. The optical absorption spectrum of these transparent MC@polymer nanocomposite films was marked by contributions from their Mo 6 and Nb 6 -based clusters (absorption in the UV range) and from the ITO layer on silica glass (absorption in the NIR range). Mo 6 @PMMA nanocomposite films also exhibited excellent photoluminescence properties, which were preserved even after exposure to 50°C at a relative humidity of 70% for one month. These films cumulate high transparency in the visible range with remarkable UV-NIR blocking properties and represent interesting candidates for functional glass application.

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Synthesis, Structure, and Properties of New Hybrid Nanocomposites Containing the [Mo₆( ₃-Cl)₈]⁴⁺Cluster

Cited by 14 publications

References 11 publications

Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride

Synthesis and reactivity of metal-containing monomers. Part 59. Preparation and polymerization transformations of vinyl and isopropenyl derivatives of hafnocene dichloride

Inorganic Molybdenum Octahedral Nanosized Cluster Units, Versatile Functional Building Block for Nanoarchitectonics

Transparent functional nanocomposite films based on octahedral metal clusters: synthesis by electrophoretic deposition process and characterization

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