Antenna dendrimer

Two practical advantages of luminescence species engulfed in antenna dendrimer scaffolds are apparent, namely their miscibility with organic media (solvents or/and resins) and their ability to form thin films. For example the lanthanide-cored dendrimer complexes described in this chapter can be regarded as organic-soluble inorganic luminescers. 

Methanofullerene 20 with phenylacetylene dendrimer addends has also been reported [45] (Fig. 10). The UV absorption of fullerodendrimer 20 is particularly strong and is mainly attributed to transitions located on the two dendritic branches of the molecule. The photophysical investigations revealed that the large poly(aryl)acetylene branches act as photon antennae [46]. 

The properties of these rotaxane dendrimers are quite different from those of the individual rotaxanes or dendrimers and often a blend of both. In view of the versatile characteristics that a dendron or dendrimer can manifest, several new properties can be imparted to the rotaxanes. For example, the solubility of rotaxanes in organic solvents as well as in water can be significantly improved when large dendrimer units are appended enhancing the prospects of their use as molecular machines. The dendritic units can also influence the photo/electro-chemical properties of the rotaxanes. Employing photo-receptive dendron units, photo chemically driven molecular machines may be developed, where the dendrons act as antenna for photo-harvesting [62]. 

Very interesting antenna systems have been constructed by functionalizing the chain ends of a poly(arylether) convergent dendritic backbone with cou-marin-2 A =435 nm) and its focal point with coumarin-343 X =49Q nm) [33] dendrimer 8 represents the fourth generation. 

Luminescence experiments in dichloromethane solution indicated that the fluorescence of the phenylacetylene branches is quenched, whereas intense emission is observed from the binaphthol core. This antenna effect represents the first example of efficient (>99%) energy migration in an optically pure dendrimer. The fluorescence quantum yield increases slightly with increasing generation the values of 0.30,0.32, and 0.40 were obtained, respectively, for 10-12. 

Keywords. Dendrimer, Antenna, Photon energy. Luminescence, Metal cation... 

The morphological dependence of the antenna effect was quantitatively studied by the comparison of the three focal isomers of benzene-cored 4th-genera-tion dendrimers [7]. The energy of the photon absorbed by the dendron subunits must be dissipated either through radiative (luminescence) or nonradia-... 

Self-assembly of aromatic dendron subunits has been tried by the design of coordination to multivalent metal cations (i.e., metal-cored dendrimer complexes). Several metal-cored dendrimer complexes have successfully exhibited luminescence by antenna effects. 

Metal dendrimers containing photoactive units exhibit very interesting properties, both from a fundamental and applicative viewpoint. For example, well-designed photoactive dendrimers can play the role of artificial antennae in supra-molecular structures devoted to solar energy conversion [37,47]. Photophysical... 

Kawa, M., and Frechet, J.M.J. (1998) Self-assembled lanthanide-cored dendrimer complexes enhancement of the luminescence properties of lanthanide ions through site-isolation and antenna effects. Chem. Mater. 10, 286-296. 

Since the properties of the modular components are known and different modules can be located in the desired positions of the dendrimer array, synthetic control of the various properties can be obtained. It is therefore possible, as schematically shown in Figure 2, to construct arrays where the electronic energy migration pattern can be predetermined, so as to channel the energy created by light absorption on the various components towards a selected module (antenna effect). 

For some reviews, see (a) Majoral J-P (2007) Influence of cationic phosphorus dendrimers on the surfactant-induced synthesis of mesostructured nanoporous silica. New J Chem 31 1259-1263 (b) Puntoriero F, Nastasi F, Cavazzini M et al (2007) Coupling synthetic antenna and electron donor species a tetranuclear mixed-metal Os(II)-Ru(II) dendrimer containing six phenothiazine donor subunits at the periphery. Coord Chem Rev... 

Kawa M, Takahagi T (2004) Improved antenna effect of terbium(III)-cored dendrimer complex and green-luminescent hydrogel by radical copolymerization. Chem Mater 16 2282-2286... 

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