Organometallic and related metal-containing dendrimers

Hearshaw, Meredith A.; Moss, John R.

doi:10.1039/a803535k

Cited by 145 publications

(60 citation statements)

References 41 publications

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“…The main aspects of this work prior to 1999 have been reviewed by Moss [5] and by Cuadrado [6]. While much of the groundwork has been laid in this specific field, many publications are still focusing on this area which extend the understanding of the interaction of the dendrimer with both the incorporated ferrocene group and other outside species, such as electrode surfaces or solutes.…”

Section: Ferrocenyl Substituted In the Periphery Of Dendrimersmentioning

confidence: 99%

“…Using methodology previously employed to assemble Fe and Ru dendrimers [5,6,20], the synthesis consists of the assembly of Fréchet-type wedges containing two rhenium centers and coupling them, through a benzylic bromide, to the 1,1,1-tris(4-hydroxyphenyl)ethane core. The structure of dendrimer 38 is shown in Fig.…”

Section: Dendrimers Containing Non-ferrocene Organometallic Groups Inmentioning

confidence: 99%

“…The reader is directed to the previously mentioned reviews and books for further information on these topics. In addition to these, a small number of reviews have detailed the research on dendrimers containing organometallic or transition metal moieties [5,6]. These reviews cover most of the major results in the field of organometallic dendrimers prior to 1999.…”

Section: Introductionmentioning

confidence: 99%

“…Since their initial conceptual development, the research and practical applications of dendritic materials has blossomed [1,2]. While most of the dendrimers synthesized to date are organic molecules [3], there has been significant effort put forward towards the incorporation of other main group elements [4], and organometallic or transition metal entities and fragments [5,6]. This merging of fields hopes to combine the properties of the organometallic or transition metal species, such as catalytic [7][8][9], electrochemical, optical and magnetic properties, with the benefits generally attributed to dendrimers, such as site isolation [10,11], precise steric environments, recyclability [12] and possible cooperative effects.…”

Section: Introductionmentioning

confidence: 99%

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Where Organometallics and Dendrimers Merge: The Incorporation of Organometallic Species into Dendritic Molecules

2005

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This review will describe the ongoing efforts being made to incorporate organometallic fragments into the framework of dendrimers. While purely dendritic organic molecules are well known and well studied, species incorporating organometallic moieties potentially offer many benefits that are not available to only organic containing dendrimers. For example, catalytic or redox active organometallic functions can be included in the dendritic framework and impart these characteristics onto the dendrimer. This report will give an overview of the latest developments in this field by highlighting selected examples that detail novel synthetic strategies or dendrimer construction methodologies, interesting practical applications or address specific problems associated with organometallic dendrimers.

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Section: Ferrocenyl Substituted In the Periphery Of Dendrimersmentioning

confidence: 99%

Section: Dendrimers Containing Non-ferrocene Organometallic Groups Inmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Where Organometallics and Dendrimers Merge: The Incorporation of Organometallic Species into Dendritic Molecules

2005

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“…transition-metal coordination polymers A, are of considerable current interest in macromolecular and supramolecular science for fundamental reasons and also because of their unusual electronical, magnetical, optical, catalytical, and solution properties [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Much effort has been spent, therefore, to broaden the diversity in which such macromolecules are available.…”

Section: Introductionmentioning

confidence: 99%

Coordination polymers from kinetically labile transitionmetal complexes: True macromolecules or only dynamic solution aggregates?

Lahn

Rehahn

2002

E-Polymers

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Readily soluble copper(I) and silver(I) coordination polymers have been prepared via the conversion of equimolar amounts of p-phenyleneethynylenebridged bis [9-(p-anisyl) 6 or AgBF 4 as their metal-monomer counterparts. The homogeneous constitution of the resulting diamagnetic macromolecules is proven using NMR spectroscopy. Their average degrees of polymerization have been shown to reach values of P n ≥ 20, and the intrinsic viscosity of the resulting randomly coiled polyelectrolytes is of the order [η] ≈ 30 mL/g in 0.01 M NH 4 PF 6 /acetone. Moreover, NMR and viscosity experiments show the chain molecules to be open solution aggregates when dissolved in coordinating solvents like acetonitrile or water. When dissolved in noncoordinating solvents, on the other hand, the multinuclear complexes were found to be "true" polymers, i.e. macromolecules with a constant number of repeating units per individual chain with respect to time. At very high dilution, transformation of the high-molecular-weight chain molecules into cyclic oligomers is observed in coordinating solvents but not in non-coordinating media.

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Inorganic Polymers

Bourke¹,

Manners²

2001

Encyclopedia of Polymer Science and Technology

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The thermal ROP route requires the synthesis and careful purification of the cyclic trimer [Cl 2 PN] 3 and the use of elevated temperatures where control of molecular weight is very difficult and cross-linking can take place at high conversion, which can limit the yield. INORGANIC POLYMERSVol. 3to phosphazene polymers, which may well facilitate more rapid and extensive commercialization.Monomer Synthesis. Both the ROP and condensation routes to poly(dichlorophosphazene) require high purity monomers. For the traditional ROP process, ultrahigh purity [NPCl 2 ] 3 is required. The most common method for its preparation is through the reaction of PCl 5 with NH 4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 • C. The yields can approach 70-80% under specialized conditions, but 50% is more typical (25). The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl 3 P NSi(CH 3 ) 3 . The synthesis of this compound has been described (21) and is based on a modification of an earlier procedure (26) involving the reaction of PCl 5 with LiN(Si(CH 3 ) 3 ) 2 at −78 • C in hexane. However, the purification required by this method is a challenge and leads to an overall yield of <40%.It has also been reported that the reaction of N(Si(CH 3 ) 3 ) 3 with PCl 5 can be manipulated to maximize yields of either the cyclic trimer (76%) or the pure phosphoranimine monomer (40%) through variations in reaction conditions (25). These reactions use milder conditions than previously reported methods, with higher yields. In addition, the major side product, (CH 3 ) 3 SiCl, can be recycled to form one of the starting materials, N(Si(CH 3 ) 3 ) 3 .N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl 3 , ((CH 3 ) 3 Si) 2 NH, and Grignard reagents by way of a three-step process, with typical yields of 60-70%. These precursors are also accessible via a "one-pot" synthesis, which requires only isolation of the final product with yields of about 75% (3).Uses. Some of the most useful polyphosphazene derivatives are fluoroalkoxy derivatives, and amorphous copolymers are very useful as flame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have found aerospace and automotive applications. Polymers such as the amorphous comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1). Vol. 3 INORGANIC POLYMERS 35Polyphosphazenes are also of interest as biomedical materials and bioinert, bioactive, membrane-forming, and bioerodable materials (1).

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Organometallic and related metal-containing dendrimers

Cited by 145 publications

References 41 publications

Where Organometallics and Dendrimers Merge: The Incorporation of Organometallic Species into Dendritic Molecules

Where Organometallics and Dendrimers Merge: The Incorporation of Organometallic Species into Dendritic Molecules

Coordination polymers from kinetically labile transitionmetal complexes: True macromolecules or only dynamic solution aggregates?

Inorganic Polymers

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