Internally functionalized dendrimers,

Facile access to internally functionalized dendrimers through efficient and orthogonal click reactions. Chem. Commun., 46, 1556-1558. 

Fig. 3.3 Premodification Growth of dendrimers starting from pre-functionalised monomeric branching units permits preparation of dendrimers with different internal functionalities in subsequent layers...

Introduction of the desired functional unit by subsequent functionalisation of the internal functionalities of the dendrimer precursor. 

As envisioned, covalent dendritic ordering can be realized by using secondary (embedded or latent) protection—deprotection schemes in concert with those already developed for dendrimer construction. For example, consider the preparation of a tetrahedrally-based dendrimer 31 possessing internal sites of attachment whereby three sites are protected and one is available for connection additional peripheral and internal functionalities are inert to the chosen attachment and deprotection conditions. Furthermore, consider the connection of two of these dendrimers to afford a bisdendrimer 32. Deprotection of the internal moieties (in no case N02 reduction) allows further dendrimer attachment, etc. (Scheme 9.4). 

Solid-Supported Internally Functionalized Chiral Dendrimer Catalysts... 

Finally, the dendrimer or star may be surface or internally functionalized or decorated with metal-containing motifs. This type of dendrimer is widely investigated with a view to preparing novel catalytic systems in which a dendritic effect results in enhanced or modified catalytic properties with respect to a similar number of mononuclear complexes. As many of these species are strictly organometaUic they do not fall properly within the scope of this volume. 

Dendrimer with peripheral and internal functionality Malkoch et... 

PAMAM dendrimers can also be used as templating agents and nanoparticle stabilizers for the synthesis of bimetallic particles. The unique ability of dendrimers to host various metal precursors enables the simultaneous complexation of multiple metallic species at its various internal functional groups. The three primary methods of bimetallic nanoparticle synthesis through dendrimer stabilization are partial displacement, co-complexation, and sequential complexation. 

Fig. 19. Anthraquinonoid dendrimers with internal modifiable functional groups...

Such a methodology is also useful for the chemoselective functionalization of internal voids of dendrimers. This can be accomplished for example by adding 2 equiv. of allyl, propargyl or phosphonate trifluoromethane sulfonate on the dendrimer of generation 1 71-lGj] (Scheme 34). Functionalization occurs on the sulfur atom of the two P=N-P(S) units with the quantitative formation of the... 

This work demonstrates that functionalization of the internal cavities of various dendrimers can be done via a post modification of the skeleton. Various functional groups can be selectively introduced aminophosphite, aldehyde, hydrazone, dichlorophosphane sulfide. Therefore all the chemistry reported on the surface of dendrimers can be now envisaged to be done into the cavities and it is demonstrated for the first time that a macromolecular chemistry can be performed into the internal voids of a dendrimer. 

Phosphorus also permits the postmodification of the backbone of dendrimers. Indeed charges, and also various functional groups, can be selectively introduced into the internal voids. Such a transformation can be performed where and when required. 

The facile functionalization of the cavities allow the development of a macro-molecular chemistry within the cascade structure of dendrimers. As an example six dendrimers of generation 4 were built into the internal voids of a dendrimer of generation 3. 

With precise functionalization, it is possible to prepare different types of dendrimer nanocomposite topologies. Balogh and Tomalia have utilized the functionalization of PAMAM dendrimers to create both external and internal... 

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