Cored dendrimers

Ionic interactions have been used to prepare lanthanide-core dendrimers. This has been achieved using a convergent synthesis, in which polyether den-drons with a carboxylic acid group at the focal point were assembled around a lanathanide cation. This involved a metathetical reaction with compounds such as Er(OAc)3, Tb(OAc)3 or Eu(OAc)3 to introduce the appropriate lanthanide ion. 

Synthetic pathways have been deliberately aimed at producing megamers. For example, poly(amido amine) dendrimers of different generations have been combined to give well-defined core-shell megamers in which a central, large core dendrimer is surrounded by a well-defined number of smaller dendrimers. 

More recently, P-cored derivative (116) was prepared from a straightforward combination of a Heck coupling, to afford an intermediate functionalised stil-bene phosphine oxide (114),a Horner-Wittig reaction yielding the phosphine oxide (115), and finally trichlorosilane reduction (Scheme 31) [89]. Using similar strategies, both the valence isoelectronic N- (117) and C- (118) cored dendrimers have been prepared (Scheme 31). 

The effect of core shielding of a porphyrin moiety by peripheral dendrons has been carefully investigated on two series of Zn-phthalocyanine-cored dendrimers with aryl-ether branches [60]. Generation 0,1, and 2 (dendrimer 27) species, terminated with ester groups, are soluble in organic solvents, while the species terminated with carboxylate units (e.g., 28) are soluble in water. 

That dendrimers are unique when compared with other architectures is confirmed by an investigation on porphyrin core dendrimers and their isomeric linear analogues [63]. The isomers displayed dramatically different hydrodynamic properties, crystallinity, and solubility characteristics when compared to those of their dendritic analogues, and photophysical studies showed that energy transfer from the poly(benzylether) backbone to the core was more efficient in the dendrimer because of the shorter distance between the donor units and the acceptor core. 

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. 

PBE dendrons bearing a focal bipyridine moiety have been demonstrated to coordinate to Ru + cations, exhibiting luminescence from the metal cation core by the excitation of the dendron subunits [28-30]. The terminal peripheral unit was examined (e.g., phenyl, naphthyl, 4-f-butylphenyl) to control the luminescence. The Ru +-cored dendrimer complexes are thought to be photo/redox-active, and photophysical properties, electrochemical behavior, and excited-state electron-transfer reactions are reported. 

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. 

The PBE dendron has a glass transition at about 40 °C and is soluble in various organic solvents (e.g., THF, acetone, toluene). It is therefore a moldable, thermoplastic, film-forming material. This practical feature is maintained for the lanthanide-cored dendrimer complexes. The complexes are partially miscible with poly(methyl methacrylate), affording transparent luminescence compositions by mixing in solvent. 

Vinylphenyl-terminated PBE dendrons were prepared as polymerizable den-drons from 4-vinylbenzyl chloride [37]. The vinylphenyl-terminated PBE dendrons are useful to make the lanthanide-cored dendrimer complexes polymerizable. The Ist-generation Tb +-cored dendrimer complex bearing the vinyl-phenyl terminal on the dendron subunits (Fig. 5) was copolymerized with N-iso-propylacrylamide in the presence of methylene bis-acrylamide (as crosslinker) in DMSO to give a green-luminescence transparent gel. The DMSO gel was con-... 

Fig. 5. A Ist-generation Tb +-cored dendrimer complex bearing polymerizable vinylphenyl groups on the dendron subunits...

The red-luminescence (612 nm) europium complex is an excellent luminescer in commercial use however, the green-luminescence Tb +-cored dendrimer complex enables a simultaneous assay at another wavelength (545 nm). The latex formation was carried out by mini-emulsion radical polymerization of the monomers dissolving the Tb +-cored dendrimer complexes. The polymeriza-... 

Fig.7. A demonstration of fluoroimmunoassay. Green circles (Tb-cored dendrimer complex) and red circles (conventional Eu complex) corresponds to different assays...

This chapter shows that the synthetic and analytical problems associated with the synthesis of the title dendrimers are not outrageously more complex than for small core dendrimers and that the difficulties can be overcome. It draws a comprehensive picture of what has been done in the field of dendrimers with polymeric cores putting emphasis first on synthetic issues and then on experiments investigating the aggregation behavior of these intruiging macromolecules both in the solid state and on surfaces. Finally, experiments will be described which show that some of these dendrimers can be considered cylindrical molecular objects. The macromolecules treated in this chapter may be... 

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. 

S-C Lo, EB Namdas, PL Burn, and IDW Samuel, Synthesis and properties of highly efficient electroluminescent green phosphorescent iridium cored dendrimers, Macromolecules, 36 9721-9730, 2003. 

Step (a) To a 500 mL round bottom flask containing a stir bar was added shell reagent (Y) G = 3.5 methyl ester PAMAM dendrimer, EDA core, (32 g, 2.6 x 10-3 mol, 164 mmol ester, 25 equivalents per core dendrimer (X) and 32 g of methanol. This mixture was stirred until homogeneous. To this mixture was added lithium chloride (7 g, 166 mmol, 1 equivalent per ester) and stirred until homogenous. To this mixture was added (drop-wise) PAMAM dendrimer, EDA core, G = 6 (6 g, 1.0 x 10-4 mol) in 20g of methanol in 10 min. This mixture was warmed to 25 °C and placed in a constant temperature bath at 40 °C for 25 days. 

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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