Organometallic dendritic macromolecules

Cuadrado, Isabel; Morán, Moisés; Losada, José; Casado, Carmen M.; Pascual, C.; Alonso, Beatriz; Lobete, Francisco

doi:10.1016/s1874-5229(96)80007-4

Cited by 64 publications

(65 citation statements)

References 84 publications

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“…[2±4] Recent reviews have indeed focused on metallodendrimers with promising functions and potential. [5±7] In particular, redox-active metallodendrimers such as polypyridine dendrimers prepared by the groups of Balzani, [8] Puddephat [9] and Constable, [10] ferrocenyl dendrimers prepared by Cuadrado et al [11,12] and tetrathiafulvalene dendrimers prepared by the groups of Bryce and Becher [13,14] illustrate the potential access to precise redox-active nanoscopic molecules with original functions. Several other groups have also reported ferrocenyl dendrimers in which the ferrocenyl group is located at the center [15] or at the periphery [16±22] of the dendrimer.…”

Section: Introductionmentioning

confidence: 99%

Molecular Batteries: Ferrocenylsilylation of Dendrons, Dendritic Cores, and Dendrimers: New Convergent and Divergent Routes to Ferrocenyl Dendrimers with Stable Redox Activity

et al. 2000

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The ferrocenylsilylation of the phenol triallyl dendron 2, of the phenol nonaallyl dendron 4, and of the 9-, 27-, 81-, and 243-allyl dendrimers 7-10 (monitored by the disappearance of the signals of the olefinic protons in 1H NMR spectra) has been achieved using ferrocenyldimethylsilane 1 and Karstedt's catalyst in diethyl ether at 40 degrees C, yielding the corresponding ferrocenyl dendrons and dendrimers. An alternative convergent synthesis of the nonaferrocenyl dendron 5 was carried out by reaction of the triferrocenyl dendron 2 with a protected triododendron followed by deprotection. Reaction of the nonaferrocenyl dendron 5 with hexakis(bromomethyl)benzene gave the 54-ferrocenyl dendron 6. All the ferrocenyl dendron and dendrimers produce a chemically and electrochemically reversible ferrocenyl oxidation wave at seemingly the same potential. Stable platinum electrodes modified with the high ferrocenyl dendrimers were fabricated. The soluble orange-red ferrocenyl dendrimers can also be oxidized in CH2Cl2 by [NO][PF6] to the insoluble deep blue polyferrocenium dendrimers. For instance, the 243-ferrocenium dendrimer has been characterized by its Mossbauer spectrum, which is of the same type as that of ferrocenium itself. The ferrocenium dendrimers can be reduced without any decomposition back to the ferrocenyl dendrimer, indicating that these multielectronic redoxstable dendrimers behave as molecular batteries.

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Section: Introductionmentioning

confidence: 99%

Molecular Batteries: Ferrocenylsilylation of Dendrons, Dendritic Cores, and Dendrimers: New Convergent and Divergent Routes to Ferrocenyl Dendrimers with Stable Redox Activity

et al. 2000

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“…The divergent synthetic route starts with 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) as a tetrafunctional core (generation 0) and approximates to the valuable methodology that has been previously used by van der Made et al, 34 Zhou and Roovers, 35 Seyferth et al 36 and by our own group 6,21 for the synthesis of carbosilane dendrimers, and involves the repetition of hydrosilylation and alkenylation reactions as the growing steps.…”

Section: Synthesis and Characterization Of Cyclotetrasiloxane-based Dmentioning

confidence: 99%

“…In general the concentration of the solutions of the dendritic molecules were in the range 10 À4 -10 À3 M, and 0.1 M [Bu 4 N][PF 6 ] was used as supporting electrolyte. Coulometric measurements were made with a PAR-379 digital coulometer, using a platinum gauze as working electrode.…”

Section: Electrochemical Measurementsmentioning

confidence: 99%

“…The reaction was performed by the same method as that described for the synthesis of 1, starting from 5.73 g (3.08 mmol) of 6 -C 5 H 4 Li) (FcLi) was generated in situ via the reaction of ferrocene (8.88 g, 47.76 mmol) with 0.5 equiv of t-BuLi in THF over 1 h at À30°C. This mixture is allowed to warm to À15°C and then 2.85 g (3.98 mmol) of 1 in THF was added dropwise.…”

Section: Tmcts-3-(sicl) 16 (7)mentioning

confidence: 99%

“…6 Dendrimers are nanosized, well defined, highly branched macromolecules emanating from a central core to a periphery that becomes more dense with increasing generation number (for recent reviews on dendrimers, see, e.g., . On the basis of the well-known organotransition metal chemistry, it is clear that the incorporation of organometallic entities on the surface or within the dendritic structures represents a stimulating challenging target in both organometallics and dendrimers research 6 (Refs [13][14][15][16][17][18][19][20] give examples concerning organometallic dendrimers; see also , because it provides a unique opportunity for tailoring organometallic dendrimers to achieve desirable properties for well-defined applications (for example, as dendritic catalysts, in multielec-tron redox and photocatalytic processes, as molecular sensors, and so on).…”

Section: Introductionmentioning

confidence: 99%

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Cyclic siloxanes and silsesquioxanes as cores and frameworks for the construction of ferrocenyl dendrimers and polymers

Casado

Cuadrado

Morán

et al. 1999

Appl. Organometal. Chem.

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Starting from 1,3,5,7‐tetramethylcyclotetrasiloxane as core, novel ferrocenyl silicon‐containing dendrimers have been constructed up to the third generation, which contains 16 peripheral ferrocene moieties. As precursors of these ferrocenyl dendritic molecules, SiCl‐ and Siallyl‐terminated cyclotetrasiloxane‐based dendrimers were also built step by step, by the repetition of hydrosilylation and alkenylation reactions as growing steps. The dendritic structures have been confirmed by 1H, 13C and 29Si NMR, infrared spectroscopy, elemental analysis, mass spectrometry and vapor‐pressure osmometry. Solution electrochemical studies showed that all the ferrocenyl redox centers attached to the dendritic surface behave as independent, electronically isolated units, so that the dendrimers exchange all the electrons simultaneously at the same potential. We also describe the application of the first redox‐active ferrocenyl polymer containing an octakis(dimethylsiloxy)octasilsesquioxane framework, as a mediator in the electrocatalytic oxidation of ascorbic acid. Copyright © 1999 John Wiley & Sons, Ltd.

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Metal‐Containing Polymers

Abd‐El‐Aziz

2012

Encyclopedia of Polymer Science and Technology

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Organometallic dendritic macromolecules

Cited by 64 publications

References 84 publications

Molecular Batteries: Ferrocenylsilylation of Dendrons, Dendritic Cores, and Dendrimers: New Convergent and Divergent Routes to Ferrocenyl Dendrimers with Stable Redox Activity

Molecular Batteries: Ferrocenylsilylation of Dendrons, Dendritic Cores, and Dendrimers: New Convergent and Divergent Routes to Ferrocenyl Dendrimers with Stable Redox Activity

Cyclic siloxanes and silsesquioxanes as cores and frameworks for the construction of ferrocenyl dendrimers and polymers

Metal‐Containing Polymers

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