Dendrimers fullerene

Keywords. Dendrimers, Fullerenes, Optical limitation. Photophysical properties, Thin films... 

Figure 7.52. Schematic of a PAMAM dendrimer-fullerene conjugate structure (top), with TGA analysis (bottom). Based on the mass loss of the conjugate, it is suggested that each PAMAM dendrimer is surrounded by 30 fullerene units. Reproduced with permission from Jensen, A. W. Maru, B. S. Zhang, X. Mohanty, D. K. Fahlman, B. D. Swanson, D. R. TomaUa, D. A. Nano Lett. 2005, 5, 1171. Copyright 2005 American Chemical Society.

Wooley et al.234 reported the first dendrimer— fullerene hybrid, 165 (Scheme 21), via the alkylation of a prederivatized fullerene diphenol, 166, with the dendritic bromide 6. Because of purification problems related to impure fullerene starting material, Hawker et al. later investigated the direct cycloaddition235 of a fourth generation azide-functionalized Frechet-type dendron, 167, with Ceo- This dendritic fullerene, 168, could be easily isolated by flash chromatography and showed a significant increase in solubility over the parent fullerene. Avent et al. reported a similar cycloaddition of poly(phenylacetylene) dendrons bearing a focal tosylhydrazone functionality.236... 

Figure 4 (a) Organic dendrimers Fullerene-based dendrimer. (Reproduced -with permission from Ref. 44. Royal Society of Chemistry, 2009.) (b) Zn Porphyrin-based... 

Dendrimer-(Fullerene) [S-l (H-5) ] Core-Shell-Type Nanocompounds... 

Carbon-rich molecules such as alkynylated ir-systems are among those molecules that attract significant attention. These molecules are related to dendrimers, fullerenes, and carbon nanotubes. They can be used as precursors to novel aromatic systems, molecular wires, or NLO active materials. 

Entries on new materials, including re-cyclate plastics, fullerenes, hard-surfaced polymers, dendrimers, transflective materials, rapid prototyping materials, silicone nitride, supercritical fluids, bulk molding compounds, conversion coatings, folic acid, replacements for chloro-fluorocarbons ... 

Fullerenes possess electronic and photophysical properties which make them natural candidates for the preparation of functional dendrimers. The attachment of a controlled number of dendrons on a core provides a compact insulating layer around the carbon sphere, and the... 

The ability of a dendritic shell to encapsulate a functional core moiety and to create a specific site-isolated microenvironment capable of affecting the molecular properties has been intensively explored in recent years [19]. A variety of experimental techniques have been employed to evidence the shielding of the core moiety and to ascertain the effect of the dendritic shell [19, 20]. Dendrimers with a fullerene core appear to be appealing candidates to evidence such effects resulting from the presence of the surrounding dendritic branches. Effectively, the lifetime of the first triplet excited state of fullerene derivatives... 

Both energy and electron transfer quenchers have been employed to show that the quenching rates of the fullerene triplet state are decreased as a function of the size of the dendrimer shell [36]. These results further demonstrate that fullerene is an excellent functional group to probe the accessibility of a dendrimer core by external molecules. 

Light-Harvesting Dendrimers with a Fullerene Core... 

All the fullerene-containing dendrimers reported to date have been prepared with a Cgo core but never with fullerene units at their surface or with Cgg spheres in the dendritic branches. We have recently started a research program on the synthesis of dendrons substituted with fullerene moieties. These fulleroden-drons are interesting building blocks for the preparation of monodisperse fullerene-rich macromolecules. In addition, they are also amphiphilic compounds capable of forming stable Langmuir films at the air-water interface. 

In a recent study, poly(aryl ether) dendritic branches terminated with triethyleneglycol chains were attached to Cgg [66] dendrimer 32 represents the fourth generation. The photophysical properties of these fullerodendrimers have been systematically investigated in three solvents, namely toluene, dichloromethane, and acetonitrile. On increasing dendrimer generation, it has been found that in each solvent (i) the maximum of the fullerene fluorescence band is red-shifted... 

The following sections discuss many of the major particle types and provide bioconjugation options for the coupling of ligands to the surface of functionalized particles. Some additional nanoparticle constructs, including gold particles, dendrimers, carbon nanotubes, Buckyballs and fullerenes, and quantum dots are discussed more fully elsewhere (see Chapter 7 Chapter 9, Section 10 Chapter 15 and Chapter 24). 

Dendrimers have also been found useful in the construction of thin films containing isolated fullerenes [85, 86]. Such materials could eventually find practical application in sensors and/or optoelectronic devices [87]. Generally, monolayers prepared from C60 are ill-defined due to the aggregation tendency of fullerenes. The covalent attachement of C60 to bulky dendritic frameworks... 

Braun M, Atalick S, Guldi Dirk M, Lanig H, Brettreich M, Burghardt S, Hatzimarinaki M, Ravanelli E, Prato M, Van Eldik R, Hirsch A (2003) Electrostatic Complexation and Photoinduced Electron Transfer between Zn-Cytochrome c and Polyanionic Fullerene Dendrimers. Chem. Eur. J. 9 3867-3875. 

Covalent functionalization of fullerenes has also been used to obtain surface-modified fullerenes that are more compatible to polymer matrices in order to fabricate composites. In this context, four basic strategies were developed. The first one allows the fullerenes to react during the monomer polymerization, so that the fullerene can be attached to the polymer chain [111, 112]. Second, an already synthesized polymer is treated using specific conditions that allow the chemical reaction with fullerenes [113,114]. Third, the fullerenes are chemically bonded to a monomer which is polymerized or co-polymerized to obtain the modified monomer [115,116]. Fourth, a dendrimer can be synthesized around a fullerene which then acts as a nucleus [117,118]. 

Reaction of 217 with Cjq leads to the amino-protected porphyrin-fulleropyrroli-dine, which can easily be deprotected to the corresponding amine [229, 277]. By further functionalization via amide coupling an easy access to extended donor-acceptor systems is possible. A carotene-porphyrin-fullerene triad was prepared by reaction of the amine with the appropriate carotene acid chloride. The motivation for the synthesis of all these donor-acceptor systems is the attempt to understand and imitate the photosynthetic process. On that score, a model for an artificial photosynthetic antenna-reaction center complex has been achieved by attaching five porphyrin cores in a dendrimer-like fashion to the fullerene [242]. 

---