Poly dendrimers, porphyrin

Stapert, H. R., Nishiyama, N., Kataoka, K., Jiang, D.-L., Aida, T., 2000, Poly-ion complex micelles encapsnlating light-harvesting dendrimer porphyrins. Langmuir 16 8182-8188. 

A poly(L-lysine) dendrimer 23 which carries 16 free-base porphyrins in one hemisphere and 16 Zn porphyrins in the other has been synthesized and studied in dimethylformamide solution [54]. In such a dendrimer, energy transfer from the Zn porphyrins to the free-base units can occur with 43% efficiency. When the 32 free base and zinc porphyrins were placed in a scrambled fashion, the efficiency of energy transfer was estimated to be 83% [55]. Very efficient (98%) energy transfer from Zn to free-base porphyrins was also observed in a rigid, snowflake-shaped structure in which three Zn porphyrin units alternate with three free-base porphyrin units [56]. 

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. 

Other supramolecular structures such as dendrimers have also been synthesized with zinc-containing porphyrins. Sixteen free base and sixteen zinc porphyrin units were added at the fifth generation of dendritic poly(L-lysine) and intramolecular fluorescence energy transfer was observed.823 Assembly of supramolecular arrays in the solid state has been achieved with the incorporation of an amide group for hydrogen bonding. Zinc meso-tetra(4-amidophenyl)porphyrin... 

Figure 13.13 Poly(aryl ether) dendrimers with a porphyrin core and dendritic imidazoles...

Similarly, a series of hydroxy-terminated poly(ether) dendrimers, 35, with a single carborane nucleus at their core, were observed to have water solubilities comparable to that of chloroacetic acid, or D,L-valine. Again this is in direct contrast to the starting carborane nucleus which is insoluble in aqueous solutions and permitted the use of 35 in neutron capture therapy. Similar effects have also been observed with dendrimers containing calixarenes [66] and porphyrins [67] as the central units. 

Scheme 18 Porphyrin dendrimers containing poly(phenylene) dendrons by Shirai and coworkers [67]...

Star-shaped multi-porphyrin arrays have been constructed to mimic energy funneUng in photosynthesis. These dendrimers contain free-base porphyrin cores (Pfb) connected to four dendrons consisting of 1,3, or 7 zinc-metallated porphyrins (Pzn) embedded in an organic matrix coimected by ether linkages (Scheme 21) [70,71]. The periphery consists of methoxy-terminated poly(aryl ether) dendrons. For comparison, cone-shaped arrays consisting of Pfb cores monosubstituted with Pz dendrons were also synthesized. 

Scheme 23 Porphyrins on the periphery of poly(L-lysine) dendrimers by Nishino and coworkers [73,74]...

FIGURE 5.13 Poly(propylene imine) dendrimers with peripheral Zn-metallated porphyrins. 

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